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Calorimetry, reflectivity and magnetism techniques were used for analyzing the transition temperature modifications with tungsten substitution. Findings reveal a significant increase in the temperature transition in a parallel way for the heating and cooling mode on substitution of molybdenum for tungsten.

High-resolution X-ray diffraction and polarized neutron diffraction experiments is performed on the Y-semiquinonate complex, Y(HBPz3)2(DTBSQ), in order to determine the charge and spin densities in the paramagnetic ground state, S=1/2. The aim of these combined studies is to bring new insights to the antiferromagnetic coupling mechanism between the semiquinonate radical and the rare earth ion in the isomorphous Gd(HBPz3)2(DTBSQ) complex.

Abstract: Sub-50nm spherical particles that exhibit single-molecule magnet (SMM) behaviour have been fabricated by direct precipitation of [Mn12O12(CH3COO)16(H2O)4] clusters in a mixture of acetonitrile and toluene. The magnetic properties clearly indicate that particle formation does not affect the molecular composition of Mn12O12 clusters, although some interesting differences appear when the magnetic behaviour exhibited by such nanoparticles is compared with a polycrystalline sample of [Mn12O12(CH3COO)16(H2O)4]. [Copyright &y& Elsevier]

The members of the CuMo1 - xWxO4 series (0 ≤ x < 0.1) undergo a first-order phase transition at normal pressure, which can be induced by temperature. The two allotropic forms exhibit two distinguishable colors, green for the high-temperature form (a) and brownish-red for the low temperature one (γ), which opens up a new market for user-friendly temperature indicators. From X-ray diffraction and microprobe analyses as from optical properties, the tungsten substitution rate for molybdenum is limited to 12%. Beyond, a third, parasitic wolframite-type phase, CuMo0.6W0.4O6, systematically crystallizes besides the α/γCuMo0.9W0.104 compounds. Within the CuMo1 - xWxO4 solid-solution domain, the dependence of the transition temperatures was followed by calorimetry, optical reflectivity, and magnetism. On the basis of these measurements, the transition is characterized for all of the chemical compositions by a hysteresis loop of about 90 K in width with a temperature transition strongly dependent on the tungsten content. Namely, the γ → α transition can occur between 260 and 360 K, and the α → γ transition between 175 and 275 K as a function of x. The control of the α/γ transition temperatures with x is related to the larger propensity of tungsten compared to molybdenum, to adopt a tetrahedral environment. [ABSTRACT FROM AUTHOR]

Abstract: We report magnetic and photomagnetic studies on polycrystalline Nd0.7Sr0.3CoO3. Strong irreversibility in field cooled and zero field cooled data is observed. The hysteresis plot exhibits a very high coercivity at low temperatures. On photon irradiation, a decrease in the coercivity and an irreversible magnetization enhancement are observed. The analysis of all these data suggest that microscopic phase separation of competing ferromagnetism and antiferromagnetism and/or light-induced spin conversion processes among low, intermediate and high spin states of cobalt ions are responsible for all the properties. [Copyright &y& Elsevier]

Organic photovoltaics (OPV) has been considered for a long time a promising emerging solar technology. Currently, however, market shares of OPV are practically non-existent. A detailed meta-analysis of the literature published until mid-2021 is presented, focusing on one of the remaining issues that need to be addressed to translate the recent remarkable progress, obtained in devices' performance at lab-scale level, into the requirements able to boost the manufacturing-scale production. Namely, the active layer's thickness is referred to, which, together with device efficiency and stability, represents one of the biggest challenges of this technological research field. Papers describing solar cells containing non-fullerene acceptor (NFA) binary and ternary blends, as well as NFA plus fullerene acceptor (FA) ternary blends are reviewed. The common ground of all analyzed devices is their high-thickness active layers, compatible with large-area deposition techniques. By defining a new figure of merit to discuss the OPV thickness (thickness tolerance, TT), it is found that this parameter is not affected by the chemical family's nature of the active blend components. On the other hand, the analysis suggests that there are promising strategies to improve the TT, which are discussed in the conclusion section., (© 2023 Wiley-VCH GmbH.)

Organic photovoltaics (OPVs) have attracted tremendous attention in the field of thin-film solar cells due to their wide range of applications, especially for semitransparent devices. Here, we synthesize a dithiaindacenone-thiophene-benzothiadiazole-thiophene alternating donor copolymer named poly{[2,7-(5,5-didecyl-5H-1,8-dithia-as-indacenone)]-alt-[5,5-(5',6'-dioctyloxy-4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]} (PDTIDTBT), which shows a relatively wide bandgap of 1.82 eV, good mobility, and high transmittance and ambient stability. In this work, we fabricate an OPV device using monolayer graphene as top electrode. Due to the stability of PDTIDTBT in air and water, we use a wet transfer technique for graphene to fabricate semitransparent OPVs. We demonstrate OPVs based on the PDTIDTBT:Phenyl-C 61/71 -butyric acid methyl ester (PCBM) blend with maximum power conversion efficiencies (PCEs) of 6.1 and 4.75% using silver and graphene top electrodes, respectively. Our graphene-based device shows a high average visible transmittance (AVT) of 55%, indicating the potential of PDTIDTBT for window application and tandem devices. Therefore, we also demonstrate tandem devices using the PDTIDTBT:Phenyl-C 61 -butyric acid methyl ester (PC 60 BM) blend in both series and parallel connections with average PCEs of 7.3 and 7.95%, respectively. We also achieve a good average PCE of 8.26% with an average open circuit voltage (V oc ) of 1.79 V for 2-terminal tandem OPVs using this blend. Based on tandem design, an OPV with PCE of 6.45% and AVT of 38% is demonstrated. Moreover, our devices show improved shelf life and ultraviolet (UV) stability (using CdSe/ZnS core shell quantum dots [QDs]) in ambient with 45% relative humidity., Competing Interests: The authors declare no competing interest.

Low carrier mobility and lifetime in semiconductor polymers are some of the main challenges facing the field of organic photovoltaics (OPV) in the quest for efficient devices with high current density. Finding novel strategies such as device structure engineering is a key pathway toward addressing this issue. In this work, the light absorption and carrier collection of OPV devices are improved by employment of ZnO nanowire (NW) arrays with an optimum NW length (50 nm) and antireflection (AR) film with nanocone structure. The optical characterization results show that ZnO NW increases the transmittance of the electron transporting layer as well as the absorption of the polymer blend. Moreover, the as-deposited polymer blend on the ZnO NW array shows better charge transfer as compared to the planar sample. By employing PC70BM:PV2000 as a promising air-stable active-layer, power conversion efficiencies of 9.8% and 10.1% are achieved for NW devices without and with an AR film, indicating 22.5% and 26.2% enhancement in PCE as compared to that of planar device. Moreover, it is shown that the AR film enhances the water-repellent ability of the OPV device., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The two-step spin crossover in mononuclear iron(III) complex [Fe(salpm)2 ]ClO4 ⋅0.5 EtOH (1) is shown to be accompanied by a structural phase transition as concluded from (57) Fe Mössbauer spectroscopy and single crystal X-ray diffraction, with spin-state ordering on just one of two sub-lattices in the intermediate magnetic and structural phase. The complex also exhibits thermal- and light-induced spin-state trapping (TIESST and LIESST), and relaxation from the LIESST and TIESST excited states occurs via the broken symmetry intermediate phase. Two relaxation events are evident in both experiments, that is, two T(LIESST) and two T(TIESST) values are recorded. The change in symmetry which accompanies the TIESST effect was followed in real time using single crystal diffraction. After flash freezing at 15 K the crystal was warmed to 40 K at which temperature superstructure reflections were observed to appear and disappear within a 10 000 s time range. In the frame of the international year of crystallography, these results illustrate how X-ray diffraction makes it possible to understand complex ordering phenomena., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The first solvent-free crystal structure of PCBM, an organic semiconductor widely used in solvent-free nanocrystalline films in plastic solar cells, is reported and its relevance to structure-property relationships discussed. The PCBM structure, obtained from o-dichlorobenzene solvates by solvent abstraction, was solved using powder diffraction, demonstrating this possibility for functionalized fullerenes.

In the series of polymeric spin-crossover compounds Fe(X-py)(2)[Ag(CN)(2))](2) (py=pyridine, X=H, 3-Cl, 3-methyl, 4-methyl, 3,4-dimethyl), magnetic and calorimetric measurements have revealed that the conversion from the high-spin (HS) to the low-spin (LS) state occurs by two-step transitions for three out of five members of the family (X=H, 4-methyl, and X=3,4-dimethyl). The two other compounds (X=3-Cl and 3-methyl) show respectively an incomplete spin transition and no transition at all, the latter remaining in the HS state in the whole temperature range. The spin-crossover behaviour of the compound undergoing two-step transitions is well described by a thermodynamic model that considers both steps. Calculations with this model show low cooperativity in this type of systems. Reflectivity and photomagnetic experiments reveal that all of the compounds except that with X=3-methyl undergo light-induced excited spin state trapping (LIESST) at low temperatures. Isothermal HS-to-LS relaxation curves at different temperatures support the low-cooperativity character by following an exponential decay law, although in the thermally activated regime and for aX=H and X=3,4-dimethyl the behaviour is well described by a double exponential function in accordance with the two-step thermal spin transition. The thermodynamic parameters determined from this isothermal analysis were used for simulation of thermal relaxation curves, which nicely reproduce the experimental data.

The syntheses of 2,6-bis(4-chloropyrazol-1-yl)pyridine (L1), 2,6-bis(4-bromopyrazol-1-yl)pyridine (L2) and 2,6-bis(4-iodopyrazol-1-yl)pyridine (L3) by electrophilic halogenation of 2,6-bis(pyrazol-1-yl)pyridine are reported. The complex [Fe(L1)2][BF4]2 crystallises in two different solvent-free polymorphs. The tetragonal (alpha) form crystallises in a known version of the "terpyridine embrace" structure, and undergoes an abrupt spin-transition at 202 K. The orthorhombic (beta) form exhibits a modified form of the same packing motif, containing two unique iron sites in a 2 : 1 ratio. One-third of the complex molecules in that material undergo a very gradual thermal spin-crossover centred at 137 K. Comparison of the two structures implies that spin-crossover cooperativity in the alpha-polymorph is transmitted in two dimensions within the extended lattice. [Fe(L2)2][BF4]2 is isostructural with alpha-[Fe(L1)2][BF4]2 and exhibits a similarly abrupt spin-transition at 253 K. In contrast, [Fe(L3)2][BF4]2 is low-spin as a powder at 360 K and below and can be crystallised as two different solvates from acetone solution. All three compounds exhibit the LIESST effect at 10 K, with photoconversions of 40-100%. Their LIESST relaxation temperatures obey the empirical T(LIESST) = T0- 0.3T(1/2) (T0 = 150 K) law that we have previously proposed for this class of compound.

Spin crossover: The photomagnetic properties of a series of [{Fe(NCS)(py-X)}(2)(bpypz)(2)] (NCS=thiocyanate, py=pyridine, X=4-Mepy, py, 3-Mepy, 3-Clpy and 3-Brpy, and bpypz=3,5-bis(pyridine-2-yl)pyazolate) binuclear complexes are close to the antiferromagnetic response of [{Fe(NCS)(3,5-dmpy)}(3)(bpypz)(2)] (3,5-dmpy=3,5-dimethylpyrazine), which is characterised by two iron(II) metal ions in a high-spin (HS) electronic configuration (see figure).This paper describes the photomagnetic properties of a series of binuclear iron(II) complexes belonging to the [{Fe(NCS)(py-X)}(2)(bpypz)(2)] family (NCS=thiocyanate; py=pyridine; bpypz=3,5-bis(pyridine-2-yl)pyrazolate; and py-X=4-Mepy (1), py (3), 3-Mepy (4), 3-Clpy (5), and 3-Brpy (6)). All of these complexes display a complete thermal spin transition centred between 100 and 150 K, and undergo the light-induced excited-spin-state trapping (LIESST) effect at low temperatures. The T(LIESST) relaxation temperature of the photoinduced high-spin state for each compound has been determined. For all of the complexes, it has been found that the T(LIESST) curves at low temperature are close to the antiferromagnetic response of the [{Fe(NCS)(3,5-dmpy)}(2)(bpypz)(2)] (3,5-dmpy=3,5-dimethylpyridine) (7) complex that is characterised by two iron(II) metal ions in a HS electronic configuration, giving some evidence of a quantitative low spin-low spin-->high spin-high spin (LS-LS-->HS-HS) photoconversion process. Depending on the nature of the cooperativity, the kinetics have been treated with stretched exponential, simply exponential, or sigmoidal models. Interestingly, this series of dinuclear complexes follows a previously proposed linear relationship between the T(LIESST) and their thermal spin transition temperatures T(1/2): T(LIESST)=T(0)-0.3T(1/2). T(0) for these compounds is equal to 100 K. Based on this, and by using the empirical linear relationship found between the thermal spin transition and the Hammett constant, the HS-HS properties of complex 7 have been understood as a reflection of the physical impossibility that the T(LIESST) was higher than T(1/2). The close vicinity of the thermal spin-crossover phenomenon of 7 has been successfully checked by applying hydrostatic pressure.

Metal-organic sub-50 nm spherical particles that exhibit single-molecule magnet behaviour have been fabricated by direct precipitation of Mn(12)O(12) clusters in a mixture of acetonitrile and toluene.

Two new spin crossover complexes [FeL(py)(2)] (1) and [FeL(DMAP)(2)] (2) with L being a tetradentate N(2)O(2)(2-) coordinating Schiff-base-like ligand [([3,3']-[1,2-phenylenebis(iminomethylidyne)]bis(2,4-pentanedionato)(2-)-N,N',O(2),O(2)'], py = pyridine and DMAP = p-dimethylaminopyridine have been investigated using temperature-dependent susceptibility and thermogravimetric and photomagnetic measurements as well as Mössbauer spectroscopy and X-ray structure analysis. Both complexes show a cooperative spin transition with an approximately 9 K wide thermal hysteresis loop in the case of 2 (T(1/2) upward arrow = 183 K and T(1/2) downward arrow = 174 K) and an approximately 2 K wide thermal hysteresis loop in the case of the pyridine diadduct 1 (T(1/2) upward arrow = 191 K and T(1/2) downward arrow = 189 K). The spin transition was additionally followed by different temperature-scanning calorimetry and Mössbauer spectroscopy for 2, and a good agreement for the transition temperatures obtained with the different methods was found. Results from X-ray structure analysis indicate that the cooperative interactions are due to elastic interactions in both compounds. They are more pronounced in the case of 2 with very short intermolecular iron-iron distances of 7.2 A and several intense C-C contacts. The change of the spin state at the iron center is accompanied by a change of the O-Fe-O angle, the so-called bit of the equatorial ligand, from 108 degrees in the high-spin state to 90 degrees in the low-spin state. The reflectivity measurements of both compounds give at low temperature indication that at the sample surface the light-induced excited spin state trapping (LIESST) effect occurs. In bulk condition using a SQUID magnetometer the complex 2 displays some photomagnetic properties with an photoexcitation level of 60% and a T(LIESST) value of 53 K.

A highly asymmetric Ni(II) cluster [Ni(4)(OH)(OMe)(3)(Hphpz)(4)(MeOH)(3)](MeOH) (1) (H(2)phpz=3-methyl-5-(2-hydroxyphenyl)pyrazole) has been prepared and its structure determined by means of single-crystal X-ray diffraction by using synchrotron radiation. Variable-temperature bulk-magnetization measurements show that the complex exhibits intramolecular-ferromagnetic interactions leading to a spin ground state S=4 with close-lying excited states. Magnetization and high-frequency EPR measurements suggest the presence of sizable Ising-type magnetic anisotropy, with zero-field splitting parameters D=-0.263 cm(-1) and E=0.04 cm(-1) for the spin ground state, and an isotropic g value of 2.25. The presence of both axial and transverse anisotropy was confirmed through low-temperature specific heat determinations down to 300 mK, but no slow relaxation of the magnetization was observed by AC measurements down to 1.8 K. Interestingly, AC susceptibility measurements down to temperatures as low as 23 mK showed no indication of slow relaxation of the magnetization in 1. Thus, despite the presence of an anisotropy barrier (U approximately 4.21 cm(-1) for the purely axial limit), the magnetization relaxation remains extremely fast down to the lowest temperatures. The estimated quantum tunneling rate, Gamma>0.667 MHz, makes this complex a prime candidate for observation of coherent tunneling of the magnetization.

The members of the CuMo1-xWxO4 series (0alpha transition can occur between 260 and 360 K, and the alpha-->gamma transition between 175 and 275 K as a function of x. The control of the alpha/gamma transition temperatures with x is related to the larger propensity of tungsten compared to molybdenum, to adopt a tetrahedral environment.

[Fe(bpp)2][Pt(ox)2].H2O (with bpp=2,6-bis(pyrazol-3-yl)-pyridine and ox=oxalate) was prepared, and its spin crossover behavior was characterized. The two-step spin transition behavior changes over several cycles. The original behavior is restored when the sample is allowed to relax for a week. Furthermore, the ST exhibits a strong dependence on the heating and cooling rate. Heating the compound at 1 K/min leads to a spin transition with a third step and a second plateau at gammaHS approximately 0.8. Quenching the sample to 77 K also affects the spin transition behavior. The kinetic relaxation is followed after quenching and after light-induced excited spin state trapping experiments.

A comprehensive study of the photomagnetic behavior of the [Fe(L222N5)(CN)2].H2O complex has been carried out. This complex is characterized by a low-spin (LS) iron(II)-metal center up to 400 K and exhibits at 10 K the well-known Light-Induced Excited Spin State Trapping (LIESST) effect. The critical LIESST temperature (T(LIESST)) has been measured to be 105 K. The kinetics of the transition from the metastable high-spin (HS) state to the low-spin state have been determined and used for reproducing the experimental T(LIESST) curve. This study represents a second example of a fully low-spin iron(II)-metal complex up to 400 K, which can be photoexcited at low temperature with an atypical long-lived metastable HS state. This underlines the preponderant role of the inner coordination sphere for stabilizing the lifetime of the photoinduced HS state.

The complex dications in the cooperative spin-crossover compound [FeL(2)][BF(4)](2) (2,6-di(pyrazol-1-yl)pyridine) pack through pi-pi interactions into a 2-D layered structure (a "terpyridine embrace" motif). The effects of doping the larger ClO(4)(-) ion into this lattice have been investigated. The bulk solids [FeL(2)][ClO(4)](x)[BF(4)](2-x) are isostructural with [FeL(2)][BF(4)](2) when x = 0.30 and 0.98, and isostructural with (structurally distinct) [FeL(2)][ClO(4)](2) when x = 1.89. When x = 1.68, powder samples are a mixture of both phases, but crystalline material adopts purely the ClO(4)(-) structure. Increasing the perchlorate content in the lattice for 0 < or =x< or = 1.68 causes a small decrease in T(1/2) and a narrowing of hysteresis in their spin-crossover, but with no significant reduction in cooperativity. It also leads to more pronounced decreases in DeltaH [by up to 3.2(5) kJ mol(-1)] and DeltaS [by up to 10(2) J mol(-1) K(-1)] for the transition by DSC. Single crystals of formula [FeL(2)][ClO(4)](y)[BF(4)](2-y) (y = 0.44 and 1.13) are isostructural with the pure BF(4)(-) salt. While their molecular structures are indistinguishable, the distances between cations in the lattice increase in the doped materials. Weakening of intermolecular pi-pi interactions between cations is the likely reason for the reduced enthalpy of spin-crossover as x increases. However, the biggest stuctural change is an increase in the spacing between the 2-D layers with increased ClO(4)(-). These results suggest that cooperativity in this material is transmitted within the terpyridine embrace layers.

This paper describes the first material to show the well-known light-induced excited spin-state trapping (LIESST) effect, the metastable excited state of which relaxes at a temperature approaching its thermal spin-crossover. Cooling polycrystalline [FeL(2)][BF(4)](2).x H(2)O (L=2,6-bis[3-methylpyrazol-1-yl]pyridine; x=0-1/3) at 1 K min(-1) leads to a cooperative spin transition, taking place in two steps centered at 147 and 105 K, that is only 54 % complete by magnetic susceptibility. Annealing the sample at 100 K for 2 h results in a slow decrease in chi(M)T to zero, showing that the remainder of the spin-crossover can proceed, but is kinetically slow. The crystalline high- and fully low-spin phases of [FeL(2)][BF(4)](2).x H(2)O are isostructural (C2/c, Z=8), but the spin-crossover proceeds via a mixed-spin intermediate phase that has a triple unit cell (C2/c, Z=24). The water content of the crystals is slowly lost on exposure to air without causing decomposition. However, the high-spin/mixed-spin transition in the crystal proceeds at 110+/-20 K when x=1/3 and 155+/-5 K when x=0, which correspond to the two spin-crossover steps seen in the bulk material. The high-spin state of the compound is generated quantitatively by irradiation of the low-spin or the mixed-spin phase at 10 K, and in approximately 70 % yield by rapidly quenching the sample to 10 K. This metastable high-spin state relaxes back to the low-spin ground state at 87+/-1 K in one, not two, steps, and without passing through the intermediate phase. This implies that thermal spin-crossover and thermally activated high-spin-low-spin relaxation in this material become decoupled, thus avoiding the physical impossibility of T(LIESST) being greater than T(1/2).

The photomagnetic properties of the following iron(II) complexes have been investigated: [Fe(L1)2][BF4]2, [Fe(L2)2][BF4]2, [Fe(L2)2][ClO4]2, [Fe(L3)2][BF4]2, [Fe(L3)2][ClO4]2 and [Fe(L4)2][ClO4]2 (L1 = 2,6-di{pyrazol-1-yl}pyridine; L2 = 2,6-di{pyrazol-1-yl}pyrazine; L3 = 2,6-di{pyrazol-1-yl}-4-{hydroxymethyl}pyridine; and L4 = 2,6-di{4-methylpyrazol-1-yl}pyridine). Compounds display a complete thermal spin transition centred between 200-300 K, and undergo the light-induced excited spin state trapping (LIESST) effect at low temperatures. The T(LIESST) relaxation temperature of the photoinduced high-spin state for each compound has been determined. The presence of sigmoidal kinetics in the HS --> LS relaxation process, and the observation of LITH hysteresis loops under constant irradiation, demonstrate the cooperative nature of the spin transitions undergone by these materials. All the compounds in this study follow a previously proposed linear relation between T(LIESST) and their thermal spin-transition temperatures T(1/2): T(LIESST) = T(0)- 0.3T(1/2). T(0) for these compounds is identical to that found previously for another family of iron(II) complexes of a related tridentate ligand, the first time such a comparison has been made. Crystallographic characterisation of the high- and low-spin forms, the light-induced high-spin state, and the low-spin complex [Fe(L4)2][BF4]2, are described.

A new series of [mu-tris-{1,n-bis(tetrazol-1-yl)alkane-N4,N4'}iron(II)] bis(perchlorate) spin-crossover coordination polymers ([Fe(nditz)3](ClO4)2]; n = 4-9) has been synthesised and characterised. The ditetrazole bridging ligands provide octahedral symmetry at the iron(II) centres while allowing the distance between iron(II) centres to be varied. These polymers have therefore been investigated to determine the effects of spacer length on their thermal and light-induced spin-transition behaviour. An increase in the number of carbon atoms in the spacer (n) raises the thermal spin-crossover temperature, while decreasing the stability of the light-induced metastable state generated through the light-induced excited spin state trapping (LIESST) effect by irradiating the sample at 530 nm. Remarkably, however, the parity of the spacer also has an effect, enabling the series of complexes to be divided into two sub-series depending on whether the bridging ligand possesses an even or an odd number of carbon atoms. An explanation at the molecular level using the single configurational coordinate (SCC) model is presented.

The spectroscopic and magnetic properties of dioxolene complexes of zinc, copper and nickel were studied by DFT calculations on model complexes of formulas [(NH(3))(4)M(II)(SQ)](+) (M=Zn, Ni; SQ=semiquinonato) and [(NH(3))(2)Cu(II)(SQ)](+). Standard approaches such as time-dependent DFT (TDDFT), the Slater transition state (STS), and broken symmetry (BS) were found to be unable to completely account for the physical properties of the systems, and complete active space-configuration interaction (CAS-CI) calculations based on the Kohn-Sham (KS) orbitals was applied. The CAS-CI energies, properly corrected with multireference perturbation theory (MR-PT), were found to be in good agreement with experimental data. We present here a calculation protocol that has a low CPU cost/accuracy ratio and seems to be very promising for interpreting the properties of strongly correlated electronic systems in complexes of real chemical size.