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Social and occupational functioning deficits contribute to overall disability in hoarding disorder (HD), and psychiatric symptoms are likely strong contributors. In turn, social/occupational impairment and psychiatric illness are known to contribute to suicidality. However, few studies have examined the relationship between these factors. We examined these relationships in 313 treatment seeking individuals with HD, measuring hoarding severity with the Saving Inventory, Revised and functional impairment with the Activities of Daily Living for Hoarding Disorder (ADL-H). We created a composite social/occupational function variable assessing employment, cohabitation, and marriage. A path analysis was used to assess the relationship between social functioning, occupational functioning, hoarding related functional impairment in activities of daily living, hoarding severity, psychiatric burden, and suicidality in HD. At least one lifetime psychiatric comorbidity was noted in 61% of participants. High rates of unemployment, living alone, never marrying or being divorced/separated, and lifetime suicide attempts were present. Hoarding severity and hoarding-related functional impairment were associated with social/occupational impairment, and, along with psychiatric burden, with suicidality in this population. These findings suggest that thorough psychiatric evaluation and assessment of suicidality is warranted for those with HD, and that hoarding-related functional impairment is closely related to measures of real-world social functioning.

Tunable photoluminescence (PL) is one of the hot topics in current materials science, and research performed on the molecular phases is at the forefront of this field. We present the new (Et 4 N) 2 [Pt II (bph)(CN) 2 ]⋅rez3⋅ 1 / 3 H 2 O (Pt2rez3) (bph=biphenyl-2,2'-diyl; rez3=3,3",5,5"-tetrahydroxy-1,1':4',1"-terphenyl, phenylene-1,4-diresorcinol coformer, a linear quaternary hydrogen bond donor) co-crystal salt based on the recently appointed promising [Pt II (bph)(CN) 2 ] 2- luminophore. Within the extended hydrogen-bonded subnetwork [Pt II (bph)(CN) 2 ] 2- complexes and rez3 coformer molecules form two types of contacts: the rez3 O-H⋅⋅⋅N complex ones in the equatorial plane of the complex and non-typical rez3 O-H⋅⋅⋅Pt ones along its axial direction. The combined structural, PL, and DFT approach identified the rez3 O-H⋅⋅⋅Pt synthons to be crucial in promoting the noticeable uniform redshift of bph ligand centered (LC) emission compared to the LC emission of the (Et 4 N) 2 [Pt II (bph)(CN) 2 ]⋅H 2 O (Pt2) precursor, owing to the direct interference of the phenol group with the Pt II -bph orbital system via altering the CT processes within. The high-resolution emission spectra for Pt2 and Pt2rez3 were successfully reproduced at 77 K by using the Franck-Cordon expressions. The possibility to tune PL properties along the plausible continuum of rez3 O-H⋅⋅⋅Pt synthons is indicated, considering various scenarios of molecular occupation of the space above and below the complex plane., (© 2024 Wiley-VCH GmbH.)

Hoarding Disorder (HD) is a prominent and disabling neuropsychiatric condition defined by the inability to discard objects resulting in impairing levels of clutter. The prevalence rate is 2-6 % and increases with age. The aging Veteran population is a high risk group for impairment associated with HD. Medical and psychiatric comorbidities as well as associated rates of disability and poor quality of life are very common in both HD and the related disorder of OCD. We examined rates of HD and OCD diagnoses at the VA San Diego Healthcare System. Data were obtained from medical records for all Veterans with these diagnoses over 8-years and included information on medical and psychiatric care, homelessness services, and Care Assessment Needs (CAN) scores. Rates of diagnosis for both HD and OCD were well below epidemiological estimates. Veterans with HD were older, had higher rates of medical hospital admissions with longer stays; had more cardiac, neurological, and acquired medical conditions; had more psychiatric comorbidities; had more interactions with the suicide prevent team and homelessness services; and had higher CAN scores than Veterans with OCD. The low rate of diagnosis and high services utilization of Veterans with HD demonstrates an area of unmet need., Competing Interests: Declaration of competing interest The authors declare there is no conflict of interests., (Published by Elsevier B.V.)

Since the last century, we have witnessed the development of molecular magnetism which deals with magnetic materials based on molecular species, i.e., organic radicals and metal complexes. Among them, the broadest attention was devoted to molecule-based ferro-/ferrimagnets, spin transition materials, including those exploring electron transfer, molecular nanomagnets, such as single-molecule magnets (SMMs), molecular qubits, and stimuli-responsive magnetic materials. Their physical properties open the application horizons in sensors, data storage, spintronics, and quantum computation. It was found that various optical phenomena, such as thermochromism, photoswitching of magnetic and optical characteristics, luminescence, nonlinear optical and chiroptical effects, as well as optical responsivity to external stimuli, can be implemented into molecule-based magnetic materials. Moreover, the fruitful interactions of these optical effects with magnetism in molecule-based materials can provide new physical cross-effects and multifunctionality, enriching the applications in optical, electronic, and magnetic devices. This Review aims to show the scope of optical phenomena generated in molecule-based magnetic materials, including the recent advances in such areas as high-temperature photomagnetism, optical thermometry utilizing SMMs, optical addressability of molecular qubits, magneto-chiral dichroism, and opto-magneto-electric multifunctionality. These findings are discussed in the context of the types of optical phenomena accessible for various classes of molecule-based magnetic materials.

Background: There are significant public health benefits to delaying the onset of Alzheimer's disease (AD) in individuals at risk. However, adherence to brain healthy behaviors is low. The Health Belief Model proposes that specific beliefs are mediators of behavior change., Objective: To characterize health belief measures from the Science of Behavior Change Research Network (SBCRN) in an older adult population and associations between health beliefs, AD risk, and current health behaviors., Methods: A total of 172 individuals from the Rhode Island AD Prevention Registry participated. SBCRN health belief measures included assessments of future time perspective, self-efficacy, deferment of gratification, and consideration of future consequences. Outcome measures included individual AD risk index score, dementia risk awareness, and lifestyle behaviors including physical, cognitive, and social activity., Results: Participants who were older had higher scores for AD risk, lower future time perspective, and lower generalized self-efficacy (all at p < 0.001). Higher generalized self-efficacy was related to increased physical activity (p < 0.010). Higher future time perspective (p < 0.001) and generalized self-efficacy (p = 0.48) were associated with lower AD risk score. Subjective cognitive decline (SCD) was associated with lower self-efficacy, ability to delay gratification, and a less expansive future time perspective., Conclusions: Greater self-efficacy and perceived future time remaining were associated with lower AD risk and greater engagement in physical activity. SCD was associated with health beliefs that may negatively affect engagement in positive brain health behaviors. Assessment of and psychoeducation about these intrapersonal health belief constructs may be important targets for behavioral interventions to reduce AD risk.

A conjunction of Single-Molecule Magnet (SMM) behavior and luminescence thermometry is an emerging research line aiming at contactless read-out of temperature in future SMM-based devices. The shared working range between slow magnetic relaxation and the thermometric response is typically narrow or absent. We report Tb III -based emissive SMMs formed in a cyanido-bridged framework whose properties are governed by the reversible structural transformation from [Tb III (H 2 O) 2 ][Co III (CN) 6 ] ⋅ 2.7H 2 O (1) to its dehydrated phase, Tb III [Co III (CN) 6 ] (2). The 8-coordinated complexes in 1 show the moderate SMM effect but it is enhanced for trigonal-prismatic Tb III complexes in 2, showing the SMM features up to 42 K. They are governed by the combination of QTM, Raman, and Orbach relaxation with the energy barrier of 594(18) cm -1 (854(26) K), one of the highest among the Tb III -based molecular nanomagnets. Both systems exhibit emission related to the f-f electronic transitions, with the temperature variations resulting in the optical thermometry below 100 K. The dehydration leads to a wide temperature overlap between the SMM behavior and thermometry, from 6 K to 42 K. These functionalities are further enriched after the magnetic dilution. The role of post-synthetic formation of high-symmetry Tb III complexes in achieving the SMM effect and hot-bands-based optical thermometry is discussed., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

A series of four new Dy 12 dodecanuclear clusters based on azobenzene derivative ligands of salicylic acid ( L1 - L4 ) has been synthesized and characterized in the crystalline phase using X-ray diffraction on single crystal and powder, IR spectroscopy, elemental analysis, and DSC-TGA methods. It was revealed that all obtained clusters exhibit the formation of the similar metallic cluster nodes, as vertex-sharing heterocubanes, obtained from four Dy 3+ cations, three bridging hydroxyl groups, and O atoms from the salicylic ligands. The coordination geometry around the Dy(III) centers has been carefully analyzed. Whereas Dy 12 -L1 and Dy 12 -L2 with L1 and L2 containing Me and OMe groups in para positions of the phenyl rings, respectively, form similar porous 3D diamond-like molecular networks due to CH-π interactions, for Dy 12 -L3 with L3 bearing NO 2 -electron-withdrawing group, the generation of 2D molecular grids assembled by π-π staking is observed, and for Dy 12 -L4 with L4 bearing phenyl substituent, 3D hexagonal channels have been generated. The complexes Dy 12 -L1 , Dy 12 -L2 , and Dy 12 -L3 exhibit a zero-field slow magnetic relaxation effect. After UV irradiation of Dy 12 -L1 , a decrease of the magnetic anisotropy energy barrier displaying the possibility of control over magnetic properties by the external stimulus has been observed.

Covalent linker transformations in metal-organic frameworks (MOFs) enable their functionalization but often suffer from low conversions or require harsh conditions, including heating, corrosive reactants and solvents, or catalysts. In this work, using solvent-free mechanochemistry for the first time for such conversions, we demonstrate the systematic MOF pore modification with pendant hydroxyl groups and the resulting effects on the network rigidity, its luminescent properties, as well as adsorption of CO 2 and vapors of methanol, ethanol, isopropanol, D 2 O, and H 2 O. A new zinc-based heterolinker MOF (JUK-20) containing both protic luminescent units and reactive tetrazine cores was used as a model and subjected to an inverse electron-demand Diels-Alder (iEDDA) click reaction with a series of dienophiles (x) of different lengths having OH groups. From the obtained series of JUK-20(Zn)-x MOFs, a flexible material capable of luminescent humidity sensing was identified, and the influence of water on the luminescence of the material was explained by analogy with the excited-state intramolecular proton transfer (ESIPT) model. In general, our results provide guidance for designing and tuning MOFs for luminescence-based detection using a stepwise synthetic approach.

Hoarding disorder (HD) is a psychiatric condition characterized by difficulty discarding items and accumulation of clutter. Although studies have established the negative impact of HD and compulsive hoarding behavior, fewer have examined the impact on quality of life (QoL) of hoarding behavior independent of obsessive-compulsive disorder (OCD). Moreover, specific aspects of QoL such as success in work/academics or satisfaction with interpersonal relationships have not been well-investigated. In this study, we examined, in a sample of 2100 adult participants obtained from Amazon Mechanical Turk, the relationships between hoarding, OCD, and depression symptomatology and four QoL domains (success, enrichment, environment, and family) derived from a factor analysis of the Quality of Life Inventory (QoLI). We performed linear regressions to examine associations between psychiatric symptomatology and QoL domains and then conducted mediation analyses to investigate the role of depressive symptomatology in the identified relationships. We found that while hoarding and obsessive-compulsive symptoms were both negatively associated with QoL, they were associated with different domains [hoarding was significantly associated ( p < 0.05) with total QoL and all domains and uniquely associated with environment and family QoL compared to obsessive-compulsive symptoms], whereas obsessive-compulsive symptoms were only significantly associated with total, success, and enrichment QoL. However, when depressive symptoms were included in the model, hoarding no longer accounted for significant variance in the total, environment, or family QoL domains ( p > 0.05), and was less strongly associated with success or enrichment. Mediation analyses confirmed the role of depression as a complete mediator of hoarding's effect on total, environment, and family QoL, and as a partial mediator of hoarding's effect on success and enrichment QoL. Further examination of the relationship between hoarding symptoms and QoL in those with mild, moderate, and severe depression indicated that in those with more severe depression, hoarding was associated with improved QoL, indicating a possible buffering or compensatory effect. The findings suggest a differential impact of hoarding and obsessive-compulsive symptoms on QoL and emphasize the importance of considering co-morbid depressive symptoms in designing more targeted interventions. Future studies should continue to investigate these complex relationships, given the high co-morbidity of hoarding and depression., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Nguyen, Zakrzewski, Sordo Vieira and Mathews.)

Studies on molecular co-crystal type materials are important in the design and preparation of easy-to-absorb drugs, non-centrosymmetric, and chiral crystals for optical performance, liquid crystals, or plastic phases. From a fundamental point of view, such studies also provide useful information on various supramolecular synthons and molecular ordering, including metric parameters, molecular matching, energetical hierarchy, and combinatorial potential, appealing to the rational design of functional materials through structure-properties-application schemes. Co-crystal salts involving anionic d -metallate coordination complexes are moderately explored (compared to the generality of co-crystals), and in this context, we present a new series of isomorphous co-crystalline salts (PPh 4 ) 3 [M(CN) 6 ](H 3 PG) 2 ·2MeCN (M = Cr, 1 ; Fe, 2 ; Co 3 ; H 3 PG = phloroglucinol, 1,3,5-trihydroxobenzene). In this study, 1 - 3 were characterized experimentally using SC XRD, Hirshfeld analysis, ESI-MS spectrometry, vibrational IR and Raman, 57 Fe Mössbauer, electronic absorption UV-Vis-NIR, and photoluminescence spectroscopies, and theoretically with density functional theory calculations. The two-dimensional square grid-like hydrogen-bond {[M(CN) 6 ] 3- ;(H 3 PG) 2 } ∞ network features original {[M(CN) 6 ] 3- ;(H 3 PG) 4 } supramolecular cis -bis(chelate) motifs involving: (i) two double cyclic hydrogen bond synthons M(-CN⋅⋅⋅HO-) 2 Ar, {[M(CN) 6 ] 3- ; H 2 PGH}, between cis -oriented cyanido ligands of [M(CN) 6 ] 3- and resorcinol-like face of H 3 PG, and (ii) two single hydrogen bonds M-CN⋅⋅⋅HO-Ar, {[M(CN) 6 ] 3- ; H PGH 2 }, involving the remaining two cyanide ligands. The occurrence of the above tectonic motif is discussed with regard to the relevant data existing in the CCDC database, including the multisite H-bond binding of [M(CN) 6 ] 3- by organic species, mononuclear coordination complexes, and polynuclear complexes. The physicochemical and computational characterization discloses notable spectral modifications under the regime of an extended hydrogen bond network.

Individuals with Hoarding Disorder (HD) frequently complain of problems with attention and memory. These self-identified difficulties are often used as justification for saving and acquiring behaviors. Research using neuropsychological measures to examine verbal and visual memory performance and sustained attention have reported contradictory findings. Here we aim to determine the relationship between self-reported problems with memory and attention, objective memory and attention performance, and self-reported depression and anxiety symptoms in HD. Data was available for 319 individuals who participated in a treatment study of HD. Multiple regression was used to assess the relationship between self-reported complaints and objective measures, with age, education, and measures of depression and anxiety included as covariates. We found no association between self-reported memory difficulties and objective verbal or visual memory performance. Self-reported problems with attention were associated with objective attentional performance, although this relationship was partially accounted for by anxiety symptom severity. There was a small association between visual memory performance at baseline and improvements in hoardingrelated functional abilities following treatment. Improvements in subjective memory complaints pre-to-post treatment were associated with improvements in hoarding symptom severity and hoarding-related functioning. These results demonstrate a dissociation between perceived and objective functioning in HD., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The interest in the generation of photoluminescence in lanthanide(III) single-molecule magnets (SMMs) is driven by valuable magneto-optical correlations as well as perspectives toward magnetic switching of emission and opto-magnetic devices linking SMMs with optical thermometry. In the pursuit of enhanced magnetic anisotropy and optical features, the key role is played by suitable ligands attached to the 4f metal ion. In this context, cyanido complexes of d-block metal ions, serving as expanded metalloligands, are promising. We report two novel discrete coordination systems serving as emissive SMMs, {[Dy III (H 2 O) 3 (tmpo) 3 ] 2 [Pt IV Br 2 (CN) 4 ] 3 }·2H 2 O (1) and {[Dy III (H 2 O)(tmpo) 4 ] 2 [Pt IV Br 2 (CN) 4 ] 3 }·2CH 3 CN (2) (tmpo = trimethylphosphine oxide), obtained by combining Dy III complexes with uncommon dibromotetracyanidoplatinate(IV) ions, [Pt IV Br 2 (CN) 4 ] 2- . They are built of analogous Z-shaped cyanido-bridged {Dy 2 Pt 3 } molecules but differ in the coordination number of Dy III (C.N. = 8 in 1, C.N. = 7 in 2) and the number of coordinated tmpo ligands (three in 1, four in 2) which is related to the applied solvents. As a result, both compounds reveal Dy III -centred slow magnetic relaxation but only 1 shows SMM character at zero dc field, while 2 is a field-induced SMM. The relaxation dynamics in both systems is governed by the Raman relaxation mechanism. These effects were analysed using ac magnetic data and the results of the ab initio calculations with the support of magneto-optical correlations based on low-temperature high-resolution emission spectra. Our findings indicate that heteroligand halogeno-cyanido Pt IV complexes are promising precursors for emissive SMMs with the further potential of sensitivity to external stimuli that may be related to the lability of the axially positioned halogeno ligands.

The ab initio calculations were correlated with magnetic and emission characteristics to understand the modulation of properties of NIR-emissive [Yb III (2,2'-bipyridine-1,1'-dioxide) 4 ] 3+ single-molecule magnets by cyanido/thiocyanidometallate counterions, [Ag I (CN) 2 ] - ( 1 ), [Au I (SCN) 2 ] - ( 2 ), [Cd II (CN) 4 ] 2- /[Cd II 2 (CN) 7 ] 3- ( 3 ), and [M III (CN) 6 ] 3- [M III = Co ( 4 ), Ir ( 5 ), Fe ( 6 ), Cr ( 7 )]. Theoretical studies indicate easy-axis-type ground doublets for all Yb III centers. They differ in the magnetic axiality; however, transversal g -tensor components are always large enough to explain the lack of zero-dc-field relaxation. The excited doublets lie more than 120 cm -1 above the ground one for all Yb III centers. It was confirmed by high-resolution emission spectra reproduced from the ab initio calculations that give reliable insight into energies and oscillator strengths of optical transitions. These findings indicate the dominance of Raman relaxation with the power n varying from 2.93(4) to 6.9(2) in the 4 - 3 - 5 - 1 - 2 series. This trend partially follows the magnetic axiality, being deeper correlated with the phonon modes schemes of (thio)cyanido matrices.

Luminescent single-molecule magnets (SMMs) constitute a class of molecular materials offering optical insight into magnetic anisotropy, magnetic switching of emission, and magnetic luminescent thermometry. They are accessible using lanthanide(III) complexes with advanced organic ligands or metalloligands. We present a simple route to luminescent SMMs realized by the insertion of well-known organic cations, tetrabutylammonium and tetraphenylphosphonium, into dysprosium(III) borohydrides, the representatives of metal borohydrides investigated due to their hydrogen storage properties. We report two novel compounds, [n-Bu 4 N][Dy III (BH 4 ) 4 ] (1) and [Ph 4 P][Dy III (BH 4 ) 4 ] (2), involving Dy III centers surrounded by four pseudo-tetrahedrally arranged BH 4 - ions. While 2 has higher symmetry and adopts a tetragonal unit cell (I4 1 /a), 1 crystallizes in a less symmetric monoclinic unit cell (P2 1 /c). They exhibit yellow room-temperature photoluminescence related to the f-f electronic transitions. Moreover, they reveal Dy III -centered magnetic anisotropy generated by the distorted arrangement of four borohydride anions. It leads to field-induced slow magnetic relaxation, well-observed for the magnetically diluted samples, [n-Bu 4 N][Y III 0.9 Dy III 0.1 (BH 4 ) 4 ] (1@Y) and [Ph 4 P][Y III 0.9 Dy III 0.1 (BH 4 ) 4 ] (2@Y). 1@Y exhibits an Orbach-type relaxation with an energy barrier of 26.4(5) K while only the onset of SMM features was found in 2@Y. The more pronounced single-ion anisotropy of Dy III complexes of 1 was confirmed by the results of the ab initio calculations performed for both 1-2 and the highly symmetrical inorganic Dy III borohydrides, α/β-Dy(BH 4 ) 3 , 3 and 4. The magneto-luminescent character was achieved by the implementation of large organic cations that lower the symmetry of Dy III centers inducing single-ion anisotropy and separate them in the crystal lattice enabling the emission property. These findings are supported by the comparison with 3 and 4, crystalizing in cubic unit cells, which are not emissive and do not exhibit SMM behavior.

A unique family of three-dimensional (3D) luminescent Sr II -Re V metal-organic frameworks (MOFs), {[Sr II (MeOH) 5 ][Re V (CN) 4 (N)(bpen) 0.5 ]·MeOH} n [ 1·MeOH ; N 3- = nitrido ligand, bpen = 1,2-bis(4-pyridyl)ethane, and MeOH = methanol], {[Sr II (MeOH) 4 ][Re V (CN) 4 (N)(bpee) 0.5 ]·2MeOH} n [ 2·MeOH ; bpee = 1,2-bis(4-pyridyl)ethylene], and {[Sr II (bpy) 0.5 (MeOH) 2 ][Re V (CN) 4 (N)(bpy) 0.5 ]} n ( 3·MeOH ; bpy = 4,4'-bipyridine), is reported. They are obtained by the molecular self-assembly of Sr 2+ ions with tetracyanidonitridorhenate(V) metalloligands, [Re V (CN) 4 (N)] 2- , and pyridine-based organic spacers (L = bpen, bpee, bpy). Such a combination of molecular precursors results in bimetallic Sr II -Re V cyanido-bridged layers further bonded by organic ligands into pillared Hofmann-type coordination skeletons. Because of the formation of {Re V -(L)-Re V } moieties providing emissive metal-to-ligand charge-transfer states, 1·MeOH - 3·MeOH exhibit solid-state room-temperature photoluminescence tunable from green to orange by the applied organic ligand. The most stable MOF of 3·MeOH , based on the alternating {Re V -(bpy)-Re V } and {Sr II -(bpy)-Sr II } linkages, exhibits three interconvertible, variously solvated phases, methanol-solvated 3·MeOH , hydrated {[Sr II (bpy) 0.5 (H 2 O) 2 ][Re V (CN) 4 (N)(bpy) 0.5 ]·0.6H 2 O} n ( 3·H 2 O ), and desolvated {[Sr II (bpy) 0.5 ][Re V (CN) 4 (N)(bpy) 0.5 ]} n ( 3 ). Their formation was correlated with water and methanol vapor sorption properties investigated for 3·H 2 O . The solvent content affects the luminescence mainly by tuning the emission energy within the series of 3·MeOH , 3·H 2 O , and 3 . All of the obtained compounds exhibit temperature-driven modulation of luminescence, including the shift of the emission maximum and lifetime. The thermochromic luminescent response was found to be sensitive to the presence and type of solvent in the crystal lattice. This work shows that the construction of [Re V (CN) 4 (N)] 2- -based MOFs is an efficient route toward advanced solid luminophores tunable by external stimuli such as solvent or temperature.

Functional molecule-based solids built of metal complexes can reveal a great impact of external stimuli upon their optical, magnetic, electric, and mechanical properties. We report a novel molecular material, {[Eu III (H 2 O) 3 (pyrone) 4 ][Co III (CN) 6 ]}· n H 2 O ( 1 , n = 2; 2 , n = 1), which was obtained by the self-assembly of Eu 3+ and [Co(CN) 6 ] 3- ions in the presence of a small 2-pyrrolidinone (pyrone) ligand in an aqueous medium. The as-synthesized material, 1 , consists of dinuclear cyanido-bridged {EuCo} molecules accompanied by two H-bonded water molecules. By lowering the relative humidity (RH) below 30% at room temperature, 1 undergoes a single-crystal-to-single-crystal transformation related to the partial removal of crystallization water molecules which results in the new crystalline phase, 2 . Both 1 and 2 solvates exhibit pronounced Eu III -centered visible photoluminescence. However, they differ in the energy splitting of the main emission band of a 5 D 0 → 7 F 2 origin, and the emission lifetime, which is longer in the partially dehydrated 2 . As the 1 ↔ 2 structural transformation can be repeatedly reversed by changing the RH value, the reported material shows a room-temperature switching of detailed luminescent features including the ratio between emission components and the emission lifetime values.

Individuals with hoarding disorder (HD) typically perform worse than peers on neuropsychological tasks involving visual perception. Functional neuroimaging shows diffusely increased activity in the visual cortex, consistent with inefficient visual processing in HD. The temporal locus of these inefficiencies in HD is unknown. This study examined the temporal unfolding of visual event-related brain potentials (ERPs) to help better define the neurophysiological mechanisms underlying visual dysfunction in HD. Thirty-three individuals with HD and 35 healthy controls (HC) were assessed using a 64-channel EEG during a modified flanker task. Permutation-controlled analyses were conducted to detect group differences in visual evoked ERPs on a millisecond-to-millisecond basis. Bayesian ANCOVAs and linear regressions that included hoarding and age were conducted to identify the best-fit model for the identified VEPs, compared to a null model that included depression and anxiety severity. Three temporal regions (175 ms, 270 ms, and 440 ms), showed differences in amplitude between HD and HC and were consistent with ERP components N1, P1/N2, and a late negative slow wave (LNSW), respectively. After controlling for depression and anxiety, HD demonstrated an enhanced ERP amplitude at N1 and an attenuated amplitude in LNSW compared to HC but did not show differences at P1/N2. For the N1 and LNSW, there was also a primary effect of the interaction between hoarding and age. This study indicates that altered visuocortical reactivity in HD first occurs at the level of visuocortical processing after 170 ms, indicating alterations of middle and later, but not early, processing in occipitotemporal visual cortex., (© 2020 Society for Psychophysiological Research.)

Coordination complexes of lanthanide(3+) ions can combine Single-Molecule Magnetism (SMM) with thermally modulated luminescence applicable in optical thermometry. We report an innovative approach towards high performance SMM-based optical thermometers which explores tunable anisotropy and the luminescence re-absorption effect of Ho III complexes. Our concept is shown in dinuclear cyanido-bridged molecules, {[Ho III (4-pyridone) 4 (H 2 O) 2 ][M III (CN) 6 ]}· n H 2 O (M = Co, 1 ; Rh, 2 ; Ir, 3 ) and their magnetically diluted analogues, {[Ho III x Y III 1- x (4-pyridone) 4 (H 2 O) 2 ][M III (CN) 6 ]}· n H 2 O (M = Co, x = 0.11, 1@Y ; Rh, x = 0.12, 2@Y ; Ir, x = 0.10, 3@Y ). They are built of pentagonal bipyramidal Ho III complexes revealing the zero-dc-field SMM effect. Experimental studies and the ab initio calculations indicate an Orbach magnetic relaxation with energy barriers varying from 89.8 to 86.7 and 78.7 cm -1 K for 1 , 2 , and 3 , respectively. 1-3 also differ in the strength of quantum tunnelling of magnetization which is suppressed by hyperfine interactions, and, further, by the magnetic dilution. The Y III -based dilution governs the optical properties as 1-3 exhibit poor emission due to the dominant re-absorption from Ho III while 1@Y-3@Y show room-temperature blue emission of 4-pyridone. Within ligand emission bands, the sharp re-absorption lines of the Ho III electronic transitions were observed. Their strong thermal variation was used in achieving highly sensitive ratiometric optical thermometers whose good performance ranges, lying between 25 and 205 K, are adjustable by using hexacyanidometallates. This work shows that Ho III complexes are great prerequisites for advanced opto-magnetic systems linking slow magnetic relaxation with unique optical thermometry exploiting a luminescence re-absorption phenomenon., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Octacyanidometallates have been successfully employed in the design of heterometallic coordination systems offering a spectacular range of desired physical properties with great potential for technological applications. The [M(CN)8]n- ions comprise a series of complexes of heavy transition metals in high oxidation states, including NbIV, MoIV/V, WIV/V, and ReV. Since the discovery of the pioneering bimetallic {MnII4[MIV(CN)8]2} and {MnII9[MV(CN)8]6} (M = Mo, W) molecules in 2000, octacyanidometallates were fruitfully explored as precursors for the construction of diverse d-d or d-f coordination clusters and frameworks which could be obtained in the crystalline form under mild synthetic conditions. The primary interest in [M(CN)8]n--based networks was focused on their application as molecule-based magnets exhibiting long-range magnetic ordering resulting from the efficient intermetallic exchange coupling mediated by cyanido bridges. However, in the last few years, octacyanidometallate-based materials proved to offer varied and remarkable functionalities, becoming efficient building blocks for the construction of molecular nanomagnets, magnetic coolers, spin transition materials, photomagnets, solvato-magnetic materials, including molecular magnetic sponges, luminescent magnets, chiral magnets and photomagnets, SHG-active magnetic materials, pyro- and ferroelectrics, ionic conductors as well as electrochemical containers. Some of these materials can be processed into the nanoscale opening the route towards the development of magnetic, optical and electronic devices. In this review, we summarise all important achievements in the field of octacyanidometallate-based functional materials, with the particular attention to the most recent advances, and present a thorough discussion on non-trivial structural and electronic features of [M(CN)8]n- ions, which are purposefully explored to introduce desired physical properties and their combinations towards advanced multifunctional materials.

The macrocyclic ligand calix[4]arene (L1) and its sulphur-containing analogue thia[4]calixarene (L2) are promising precursors for functional molecular materials as they offer rational functionalization with various organic groups. Here, we present the first example of lanthanide-based coordination polymers built from the macrocyclic thiacalix[4]arene backbone bearing four carboxylic moieties, namely, ligand H 4 L3. The combination of H 4 L3 with the Tb 3+ and Dy 3+ cations led to the formation of 1D ladder-type coordination polymers with the formula [Ln III HL3DMF 3 ]·(DMF) (where DMF = dimethylformamide and Ln = Tb or Dy, denoted as HL3-Tb and HL3-Dy), which resulted from the coordination of the lanthanide cations with the partially deprotonated ligand HL3 3- that behaved as a T-shape connector. The coordination sphere around the metal was completed by the coordinated DMF solvent molecules. By combining both Tb 3+ and Dy 3+ cations, isostructural heterobimetallic solid solutions HL3-Tb 1- x Dy x were also prepared. HL3-Tb and HL3-Dy showed visible light photoluminescence originating from the f-f electronic transitions of pale green emissive Tb 3+ and pale yellow emissive Dy 3+ with efficient sensitization by the functionalized thia[4]calixarene ligand HL3. In the HL3-Tb 1- x Dy x solid solutions, the Tb/Dy ratio governed both the emission colour as well as the emission quantum yield, which reached even 28% at room temperature for HL3-Tb. Moreover, HL3-Dy exhibited a slow magnetic relaxation effect related to the magnetic anisotropy of the dodecahedral Dy 3+ complexes, which were well isolated in the crystal lattice by expanded organic spacers., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Lanthanide(III)-based coordination complexes have been explored as a source of bifunctional molecular materials combining Single-Molecule Magnet (SMM) behavior with visible-to-near-infrared photoluminescence. In pursuit of more advanced multifunctionality, the next target is to functionalize crystalline solids based on emissive molecular nanomagnets toward high proton conductivity and an efficient luminescent thermometric effect. Here, a unique multifunctional molecule-based material, (H 5 O 2 ) 2 (H)[Yb III (hmpa) 4 ][Co III (CN) 6 ] 2 ·0.2H 2 O ( 1 , hmpa = hexamethylphosphoramide), composed of molecular {YbCo 2 } 3- anions noncovalently bonded to acidic H 5 O 2 + and H + ions, is reported. The resulting Yb III complexes present a slow magnetic relaxation below 6 K and room temperature NIR 4f-centered photoluminescence sensitized by [Co(CN) 6 ] 3- ions. The microporous framework, built on these emissive magnetic molecules, exhibits a high proton conductivity of the H-hopping mechanism reaching σ of 1.7 × 10 -4 S·cm -1 at 97% relative humidity, which classifies 1 as a superionic conductor. Moreover, the emission pattern is strongly temperature-dependent which was utilized in achieving a highly sensitive single-center luminescent thermometer with a relative thermal sensitivity, S r > 1% K -1 in the 50-175 K range. This work shows an unprecedented combination of magnetic, optical, and electrical functionalities in a single phase working as a proton conductive NIR-emissive thermometer based on Single-Molecule Magnets.

We report an efficient pathway toward sensitization of red room temperature Eu III emission by the charge-transfer (CT) states related to d 8 -d 10 heterometallophilic interactions achieved by the simultaneous application of tetracyanidometallates of Pt II /Pd II and dicyanidometallates of Au I /Ag I in the construction of a trimetallic d-d-f assembly. The combination of Eu 3+ , [M II (CN) 4 ] 2- (M = Pt, Pd), and [M I (CN) 2 ] - (M = Au, Ag) ions along with 4,4'-bipyridine N , N '-dioxide (4,4'-bpdo) results in four novel isostructural 2D {[Eu III (4,4'-bpdo)(H 2 O) 2 ][M II (CN) 4 ]}·[M I (CN) 2 ]·H 2 O (M II /M I = Pt/Au, 1 ; Pt/Ag, 2 ; Pd/Au, 3 ; Pd/Ag, 4 ) coordination networks. They are built of hybrid coordination layers, based on cyanido-bridged {Eu III [M II (CN) 4 ]} n square grids coexisting with metal-organic {Eu III (4,4'-bpdo)} n chains, with the further attachment of [M I (CN) 2 ] - ions through metallophilic {M II -M I } interactions. This results in dinuclear {M II M I } units generating an orange emissive metal-to-metal-to-ligand charge-transfer (MMLCT) state, whose energy is tuned by the applied d 8 -d 10 metal centers. Thanks to these CT states, 1 - 4 exhibit room temperature red Eu III photoluminescence enhanced by energy transfer from {M II M I } units, with the additional role of 4,4'-bpdo also transferring the energy to lanthanides. These donor CT states lying in the visible range successfully broaden the available efficient excitation range up to 500 nm. The overall emission quantum yield ranges from 8(1)% for 4 to 15(2)% for 1 , with the intermediate values for 2 and 3 relatively high among the reported Eu III -based compounds with tetracyanido- and dicyanidometallates. We found that the sensitization efficiency is equally high for all compounds because of the similar energies of the CT states, while the main differences are related to the observed emission lifetimes ranging from ca. 80 μs for 4 to 120-130 μs for 2 and 3 to ca. 180 μs for 1 . This phenomenon was correlated with the energies of the vibrational states, e.g., cyanide stretching vibrations, responsible for nonradiative deactivation of Eu III excited states, which are the highest for the Pd/Ag pair of 4 and the lowest for the Pt/Au pair in 1 . Thus, the heaviest pair of Pt II /Au I cyanide metal complexes is proven to be the best candidate for the sensitization of room temperature Eu III luminescence.

Microporous magnets compose a class of multifunctional molecule-based materials where desolvation-driven structural transformation leads to the switching of magnetic properties. Herein, we present a special type of microporous magnet where a dehydration-hydration process within a bimetal coordination framework results in the switching of emissive Dy III single-molecule magnets (SMMs). We report a three-dimensional (3-D) cyanido-bridged coordination polymer, {[Dy III (H 2 O) 2 ][Co III (CN) 6 ]}·2.2H 2 O ( 1 ), and its dehydrated form of {Dy III [Co III (CN) 6 ]} ( 2 ), which was obtained through a reversible single-crystal-to-single-crystal transformation. Both phases are composed of paramagnetic Dy III centers alternately arranged with diamagnetic hexacyanidocobaltates(III). The hydrated phase contains eight-coordinated [Dy III (μ-NC) 6 (H 2 O) 2 ] 3- complexes of a square antiprism geometry, while the dehydrated form contains six-coordinated [Dy III (μ-NC) 6 ] 3- moieties of a trigonal prism geometry. This change in coordination geometry results in the generation of Dy III single-molecule magnets in 2 , whereas slow magnetic relaxation effect is not observed for Dy III sites in 1 . The D 4d -to- D 3h symmetry change of Dy III complexes produces also the shift of photoluminescent color from nearly white to deep yellow thanks to the modulation of emission bands of f-f electronic transitions. A combined approach utilizing dc magnetic data and low-temperature emission spectra confirmed an axial crystal field of trigonal prismatic Dy III complexes in 2 , which produces an Orbach type of slow magnetic relaxation. Therefore, we present a unique route to the efficient switching of SMM behavior and photoluminescence of Dy III complexes embedded in a 3-D cyanido-bridged framework.

Three-dimensional bimetallic cyanido-bridged frameworks, [Ln III (2,2'-bipyridine N,N'-dioxide) 2 (H 2 O)][Cu I 2 (CN) 5 ]⋅5 H 2 O (Ln=Dy, 1; Yb, 2), are reported. They exhibit the effect of slow relaxation of magnetization, leading to a magnetic hysteresis loop, and sensitized visible-to-near-infrared photoluminescence. Both physical properties are related to the eight-coordinated lanthanide(III) complexes embedded in the unprecedented coordination skeleton composed of symmetry-breaking polycyanidocuprate linkers. The three-dimensional d-f cyanido-bridged network was shown to serve as an efficient coordination scaffold to achieve emissive lanthanide single-molecule magnets., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report a unique synthetic route toward the multistep spin crossover (SCO) effect induced by utilizing the partial ligand transformation during the crystallization process, which leads to the incorporation of three different Fe II complexes into a single coordination framework. The 3-acetoxypyridine (3-OAcpy) molecules were introduced to the self-assembled Fe II -[M IV (CN) 8 ] 4- (M = Mo, Nb) system in the aqueous solution which results in the partial hydrolysis of the ligand into 3-hydroxypyridine (3-OHpy). It gives two novel isostructural three-dimensional {Fe II 2 (3-OAcpy) 5 (3-OHpy) 3 [M IV (CN) 8 ]}· nH 2 O (M = Mo, n = 0, FeMo; M = Nb, n = 1, FeNb) coordination frameworks. They exhibit an unprecedented cyanido-bridged skeleton composed of {Fe 3 M 2 } n coordination nanotubes bonded by additional Fe complexes. These frameworks contain three types of Fe sites differing in the attached organic ligands, [Fe1(3-OAcpy) 4 (μ-NC) 2 ], [Fe2(3-OHpy) 4 (μ-NC) 2 ], and [Fe3(3-OAcpy) 3 (3-OHpy)(μ-NC) 2 ], which lead to the thermal two-step Fe II SCO, as proven by X-ray diffraction, magnetic susceptibility, UV-vis-NIR optical absorption, and 57 Fe Mössbauer spectroscopy studies. The first step of SCO, going from room temperature to the 150-170 K range with transition temperatures of 245(5) and 283(5) K for FeMo and FeNb, respectively, is related to Fe1 sites, while the second step, occurring at the 50-140 K range with transition temperatures of 70(5) and 80(5) K for FeMo and FeNb, respectively, is related to Fe2 sites. The Fe3 site with both 3-OAcpy and 3-OHpy ligands does not undergo the SCO at all. The observed two-step SCO phenomenon is explained by the differences in the ligand field strength of the Fe complexes and the role of their alignment in the coordination framework. The simultaneous application of two related pyridine derivatives is the efficient synthetic route for the multistep Fe II SCO in the cyanido-bridged framework which is a promising step toward rational design of advanced spin transition molecular switches.

Unique hybrid organic-inorganic coordination networks, three-dimensional [(UO2)2(OH)(4,4'-bpdo)2][M(CN)6]·nH2O (M = Co, 1; Rh, 2; Ir, 3) and layered [(UO2)2(OH)2(4,4'-bpdo)2][Pt(CN)6]·H2O (4), employing cyanide, hydroxide and 4,4'-bpdo bridges, are reported. They exhibit vibronically coupled charge transfer emission of uranyl ions, whose colour is tunable from green to orange by the implemented hexacyanidometallates.

This study compares the effectiveness of approaches used to recruit a diverse sample for a randomized clinical trial for Hoarding Disorder (HD) in the San Francisco Bay Area. Of the 632 individuals who inquired about the study, 313 were randomized and 231 completed treatment. Most participants heard about the study via flyering (N = 161), followed by advocacy groups (N = 113), word of mouth (N = 84), health care professionals (N = 78), online (N = 68), and media (N = 11). However, those that heard about the study via advertising methods, such as flyers, were less likely to complete the study, p = .01, while those recruited via advocacy groups were most likely to be randomized, p = .03. No source proved more effective in recruiting underrepresented groups such as men, p = .60; non-whites, p = .49; or Hispanics, p = .97. Advertising recruited the youngest individuals, p < 0.001, and word of mouth was most likely to recruit unemployed, disabled, or retired individuals, p = .01. Thus, results suggest an ongoing multimodal approach is likely to be most effective in both soliciting and retaining a diverse sample. Future studies should compare recruitment methods across greater geographical regions too, as well as in terms of financial and human costs.

Hoarding disorder (HD) has been hypothesized to arise from deficits in error monitoring and abnormalities in emotional processing, but the relationship between error monitoring and emotional processing has not been examined. We examined measures of self-report, as well as behavioral, physiological, and facial responses to errors during a Stop-Change Task. 25 participants with HD and 32 healthy controls (HC) were recruited. Participants reported on number of errors committed and pre/post emotional response to errors. Skin conductance response (SCR) during correct and error commission trials was examined. Facial expression during task performance was coded for self-conscious and negative emotions. HD and HC participants had significantly different error rates but comparable error correction and post-error slowing. SCR was significantly lower for HD during error commission than for HC. During error trials, HD participants showed a significant deficit in displays of self-conscious emotions compared to HC. Self-reported emotions were increased in HD, with more negative and self-conscious emotion reported than was reported for HC participants. These findings suggest that hypoactive emotional responding at a physiological level may play a role in how errors are processed in individuals with HD., (Copyright © 2018. Published by Elsevier B.V.)