Search

Dinuclear Re(I) complexes have proportionally been much less studied than mononuclear analogues. In particular, very little information is available about their solid-state emission properties. In this work, two structural isomers of dinuclear complexes (Bi-Re-metaPhe and Bi-Re-paraPhe), which differ by the relative position of the coordination spheres on a central phenyl ring, were synthesized and compared with each other and with the parent mononuclear compound (Mono-Re-Phe), from a theoretical and experimental point of view. In solution, the electronic, electrochemical and spectroscopic properties of the dinuclear complexes were almost identical, and rather close to those of the monomer. In the solid state, the photoluminescence (PL) efficiency of dimers was not higher than that of the monomer, but a clear mechanoresponsive luminescence (MRL) effect appeared only for the former ones. The positional isomerism influenced the amplitude of this effect, as well as the aggregation-induced emission (AIE) properties in a water-acetonitrile mixture. This study reveals the importance of positional isomerism to modulate the emission properties in the solid state. It also shows the advantage of dinuclear structures to access new MRL-active materials.

The tricarbonylrhenium complexes that incorporate a mesoionic carbene ligand represent an emerging and promising class of molecules, the solid-state optical properties of which have rarely been investigated. The aim of this comprehensive study is to compare three of these complexes with their 1,2,3-triazole-based analogues. The Hirshfeld surface analysis of the crystallographic data revealed that the triazolylidene derivatives are more prone to π-π interactions than their 1,2,3-triazole-based counterparts. The FT-IR and electrochemical data indicated a stronger electron donor effect from the organic ligand to the rhenium atom for triazolylidene derivatives, which was confirmed by DFT calculations. All compounds were phosphorescent in solution, where the 1,2,3-triazole-based complexes showed unusually strong dependence on dissolved oxygen. All compounds also emitted in the solid state, some of them exhibited marked solid-state luminescence enhancement (SLE) effect. The 1,2,3-triazole based complex Re-Phe even displayed astounding photoluminescence efficiency with quantum yield up to 0.69, and proved to be an excellent candidate for applications linked to aggregation-induced emission (AIE). Interestingly, one triazolylidene-based complex (Re-T-BOP) showed attractive antibacterial activity. This study highlights the potential of these new molecules for applications in the fields of photoluminescent and therapeutic materials, and provides the first bases for the design of efficient molecules in these research areas.

Slightly different reaction conditions afforded two distinct cavity-shaped cis-chelating diphosphanes from the same starting materials, namely diphenyl(2-phosphanylphenyl)phosphane and an α-cyclodextrin-derived dimesylate. Thanks to their metal-confining properties, the two diphosphanes form only mononuclear [CuX(PP)] complexes (X=Cl, Br, or I) with the tricoordinated metal ion located just above the center of the cavity. The two series of Cu I complexes display markedly different luminescence properties that are both influenced by the electronic properties of the ligand and the unique steric environment provided by the cyclodextrin (CD) cavity. The excited state lifetimes of all complexes are significantly longer than those of the cavity-free analogues suggesting peculiar electronic effects that affect radiative deactivation constants. The overall picture stemming from absorption and emission data suggests close-lying charge-transfer (MLCT, XLCT) and triplet ligand-centered (LC) excited states., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Since intramolecular π-π stacking interactions can modify the geometry, crystal packing mode, or even the electronic properties of transition metal complexes, they are also likely to influence the solid-state luminescence properties. Following this concept, a new tricarbonylrhenium(I) complex (Re-BPTA) was designed, based on a simple symmetrical 5,5'-dimethyl-4,4'-diphenyl-3,3'-bi-(1,2,4-triazole) organic ligand. The complex was prepared in good yield using a three-step procedure. The crystallographic study revealed that both phenyl rings are located on the same side of the molecule, and twisted by 71° and 62°, respectively, with respect to the bi-(1,2,4-triazole) unit. They overlap significantly, although they are slipped parallel to each other to minimize the intramolecular interaction energy. The π-π stacking interaction was also revealed by 1 H NMR spectroscopy, in good agreement with the results of theoretical calculations. In organic solutions, a peculiar electrochemical signature was observed compared to closely-related pyridyl-triazole (pyta)-based complexes. With regard to the optical properties, the stiffness of the Re-BPTA complex led to the stabilization of the 3 MLCT state, and thus to an enhancement of the red phosphorescence emission compared to the more flexible pyta complexes. However, an increased sensitivity to quenching by oxygen appeared. In the microcrystalline phase, the Re-BPTA complex showed strong photoluminescence (PL) emission in the green-yellow wavelength range ( λ PL = 548 nm, Φ PL = 0.52, 〈 τ PL 〉 = 713 ns), and thus a dramatic solid-state luminescence enhancement (SLE) effect. These attractive emission properties can be attributed to the fact that the molecule undergoes little distortion between the ground state and the triplet excited state, as well as to a favorable intermolecular arrangement that minimizes detrimental interactions in the crystal lattice. The aggregation-induced phosphorescence emission (AIPE) effect was clear, with a 7-fold increase in emission intensity at 546 nm, although the aggregates formed in aqueous medium were much less emissive than the native microcrystalline powder. In this work, the rigidity of the Re-BPTA complex is reinforced by the intramolecular π-π stacking interaction of the phenyl rings. This original concept provides a rhenium tricarbonyl compound with very good SLE properties, and could be used more widely to successfully develop this area of research.

A β-cyclodextrin-based diphosphane with metal-confining properties was efficiently synthesized thanks to an unprecedented Smiles-like rearrangement of diphenyl-(2-phosphanylphenyl)phosphane in the presence of excess n-BuLi. The cis-chelating bidentate ligand is capable of forming very stable heteroleptic [Cu(NN)(PP)] + complexes in which a metal-bound diimine ligand (bpy, phen, or mmp) is located within the cyclodextrin cavity. As a result of ligand encapsulation, flattening of the metal tetrahedral geometry in the excited state is disfavored, thereby resulting in enhanced luminescent properties., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Tricarbonylrhenium(I) complexes that incorporate a chloride ligand are promising photoluminescent materials, but those incorporating a bromide or iodide ligand have received very little attention regarding their solid-state properties. In this work, three rhenium(I) complexes differing only by the nature of their halide ligand (X = Cl, Br, and I) were compared. They are based on a fac-[ReX(CO) 3 (N^N)] framework where the N^N bidentate ligand is a 3-(2-pyridyl)-1,2,4-triazole unit functionalized by an appended phenyl group. DFT calculations showed that the character of the lowest energy transitions progressively changes from Re → N^N ligand (MLCT) to X → N^N ligand (XLCT) when increasing the size of the halogen atom. Regarding the electrochemical behavior, the chloride and bromide complexes 1-Cl and 1-Br were similar, while the iodide complex 1-I exhibited a strikingly different electrochemical signature in oxidation. From a spectroscopic viewpoint, all three complexes emitted weak red-orange phosphorescence in dichloromethane solution. However, in the solid state, marked differences appeared. Not only was 1-Cl a good emitter of yellow light, but it had strong solid-state luminescence enhancement (SLE) properties. In comparison, 1-Br and 1-I were less emissive and they showed better mechanoresponsive luminescence (MRL) properties, probably related to a loose molecular arrangement in the crystal packing and to the opening of vibrational non-radiative deactivation pathways. This study highlights for the first time how the nature of the halide ligand in this type of complex allows fine tuning of the solid-state optical properties, for potential applications either in bio-imaging or in the field of MRL-active materials., (© 2022. The Author(s), under exclusive licence to European Photochemistry Association, European Society for Photobiology.)

Strongly luminescent tricarbonylrhenium(I) complexes are promising candidates in the field of optical materials. In this study, three new complexes bearing a 3-(2-pyridyl)-1,2,4-triazole (pyta) bidentate ligand with an appended phenyl group were obtained in very good yields owing to an optimized synthetic procedure. The first member of this series, i.e. complex 1, was compared with the previously studied complex RePBO to understand the influence of the fluorescent benzoxazole unit grafted on the phenyl ring. Then, to gauge the effect of steric hindrance on the luminescence properties, the phenyl group of complex 1 was substituted in the para position by a bulky tert -butyl group or an adamantyl moiety, affording complexes 2 and 3, respectively. The results of theoretical calculations indicated that these complexes were quite similar from an electronic point of view, as evidenced by the electrochemical study. In dichloromethane solution, under excitation in the UV range, all the complexes emitted weak phosphorescence in the red region. In the solid state, they could be excited in the blue region of the visible spectrum and they emitted strong yellow light. The photoluminescence quantum yield was markedly increased with raising the size of the substituent, passing from 0.42 for 1 to 0.59 for 3. The latter complex also exhibited clear waveguiding properties, unprecedented for rhenium complexes. From this point of view, these easy-synthesized and spectroscopically attractive complexes constitute a new generation of emitters for use in imaging applications and functional materials. However, the comparison with RePBO showed that the presence of the benzoxazole group leads to unsurpassed mechanoresponsive luminescence (MRL) properties, due to the involvement of a unique photophysical mechanism that takes place only in this type of complex.

Mechanoresponsive luminescence (MRL) materials promise smart devices for sensing, optoelectronics and security. We present here the first report on the MRL activity of two Re I complexes, opening up new opportunities for applications in these fields. Both complexes exhibit marked solid-state luminescence enhancement (SLE). Furthermore, the pristine microcrystalline powders emit in the yellow-green region, and grinding led to an amorphous phase with concomitant emission redshift and shrinking of the photoluminescence (PL) quantum yields and lifetimes. Quantum chemical calculations revealed the existence of two low-lying triplet excited states with very similar energy levels, that is, 3 IL and 3 MLCT, having, respectively, almost pure intraligand (IL) and metal-to-ligand charge-transfer (MLCT) character. Transition between these states could be promoted by rotation around the pyridyltriazole-phenylbenzoxazole bond. In the microcrystals, in which rotations are hindered, the 3 IL state induces the prominent PL emission at short wavelengths. Upon grinding, rotation is facilitated and the transition to the 3 MLCT state results in a larger proportion of long-wavelength PL. FTIR and variable-temperature PL spectroscopy showed that the opening of the vibrational modes favours non-radiative deactivation of the triplet states in the amorphous phase. In solution, PL only arises from the 3 MLCT state. The same mechanism accounts for the spectroscopic differences observed when passing from crystals to amorphous powders, and then to solutions, thereby clarifying the link between SLE and MRL for these complexes., (© 2020 Wiley-VCH GmbH.)

Dendrimers are hyperbranched macromolecules, which are synthesized step-by-step by the repetition of a series of reactions. While many different types of dendrimers are known, this review focusses on the use of trivalent phosphorus derivatives (essentially phosphines and phosphoramidites) for the synthesis of dendrimers. The first part presents dendrimers constituted of phosphines at each branching point. The other parts display the use of trivalent phosphorus derivatives during the synthesis of dendrimers. Different types of reactions have been applied to phosphines. The very first examples of phosphorus-containing dendrimers were obtained by the alkylation of phosphines. Then, several families of dendrimers were elaborated by reaction of phosphoramidites. Such a type of reaction is the base of the solid phase synthesis of oligonucleotides; it has been applied in particular for the synthesis of dendrimers constituted of oligonucleotides. Finally, the Staudinger reaction between phosphines and azides afforded different families of dendrimers, and was at the origin of accelerated methods of synthesis of dendrimers. Besides, the reactivity of the P=N-P=S linkages created by this reaction led to very original dendritic structures.

In order to improve the remarkable performance of a mononuclear tricarbonyl rhenium(i) complex (ReL1) that exhibits rare aggregation-induced phosphorescence enhancement (AIPE) behavior, two new complexes (ReL3 and ReL4) were prepared and investigated. They incorporate a 2-pyridyl-1,2,4-triazole (pyta) ligand connected to a 2-phenylbenzoxazole (PBO) moiety. Complex ReL3 differs from ReL1 by the presence of a bulky tert-butyl substituent, and ReL4 is an isomer where the PBO group is linked to the pyta ligand by its phenyl group. Theoretical calculations were in congruence with electrochemical and spectroscopic properties in solutions. Both new compounds exhibited strong AIPE and much better solid-state emission efficiency than ReL1, with photoluminescence quantum yields up to 55% for ReL4. Crystallographic data indicate that this increase in emission efficiency is due to optimum packing that prevents quenching. This work shows that minor structural changes may have major effects upon the solid-state spectroscopic properties and it provides a rational basis for accessing AIPE-active strongly emissive rhenium(i) complexes.

Heteroleptic copper(I) complexes combining phenanthroline derivatives (NN) and chelating bisphosphine ligands (PP) are an important class of luminescent materials for various applications. Although thermodynamically stable, [Cu(NN)(PP)] + derivatives are also kinetically unstable. As a result, a dynamic ligand-exchange reaction is often observed in solution, leading to a dynamic mixture of heteroleptic and homoleptic complexes. To prevent the formation of the homoleptic species, macrocyclic phenanthroline ligands have been used for the preparation of [Cu(NN)(PP)] + pseudorotaxanes. The topological constraint resulting from the macrocyclic structure of the NN ligand drives the thermodynamic equilibrium towards the exclusive formation of the heteroleptic complex as long as the macrocycle is large and flexible enough to allow for the threading of the PP ligand. Conversely, when the threading is prevented by steric constraints, unprecedented copper(I) complexes with a trigonal coordination geometry are obtained. These results are summarized in the present concept article., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The electronic and structural properties of ten heteroleptic [Cu(NN)(PP)] + complexes have been investigated. NN indicates 1,10-phenanthroline (phen) or 4,7-diphenyl-1,10-phenanthroline (Bphen); each of these ligands is combined with five PP bis-phosphine chelators, i.e., bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)benzene (dppb), and bis[(2-diphenylphosphino)phenyl] ether (POP). All complexes are mononuclear, apart from those based on dppm, which are dinuclear. Experimental data-also taken from the literature and including electrochemical properties, X-ray crystal structures, UV-vis absorption spectra in CH 2 Cl 2 , luminescence spectra and lifetimes in solution, in PMMA, and as powders-have been rationalized with the support of density functional theory calculations. Temperature dependent studies (78-358 K) have been performed for selected complexes to assess thermally activated delayed fluorescence. The main findings are (i) dependence of the ground-state geometry on the crystallization conditions, with the same complex often yielding different crystal structures; (ii) simple model compounds with imposed C 2 v symmetry ([Cu(phen)(PX 3 ) 2 ] + ; X = H or CH 3 ) are capable of modeling structural parameters as a function of the P-Cu-P bite angle, which plays a key role in dictating the overall structure of [Cu(NN)(PP)] + complexes; (iii) as the P-Cu-P angle increases, the energy of the metal-to-ligand charge transfer absorption bands linearly increases; (iv) the former correlation does not hold for emission spectra, which are red-shifted for the weaker luminophores; (v) the larger the number of intramolecular π-interactions within the complex in the ground state, the higher the luminescence quantum yield, underpinning a geometry locking effect that limits the structural flattening of the excited state. This work provides a general framework to rationalize the structure-property relationships of [Cu(NN)(PP)] + , a class of compounds of increasing relevance for electroluminescent devices, photoredox catalysis, and solar-to-fuels conversion, which so far have been investigated in an unsystematic fashion, eluding a comprehensive understanding.

Two isomeric tricarbonyl rhenium(i) complexes, ReL1 and ReL2, that possess a 2-pyridyl-1,2,n-triazole (pyta) ligand (n = 4 and 3, respectively) connected to a 2-phenylbenzoxazole (PBO) moiety, were synthesized in good yields. The X-ray structures showed that in ReL1 the PBO moiety and the pyta ligand almost form a right angle hindering electron delocalization, while in ReL2 their nearly planar arrangement favors the electron delocalization in the whole organic ligand. Therefore, the nature of the ligand significantly influences the electron distribution in the two complexes, as indicated by the results of TD-DFT calculations. An electrochemical study highlighted that, by comparison with ReL2, the smaller HOMO-LUMO energy gap of ReL1 is in line with its lower first reduction potential. From a spectroscopic viewpoint, both complexes emitted phosphorescence in organic solvents, with distinct color and intensity. They also emitted in the solid state, but only ReL1 showed significant aggregation-induced phosphorescence emission (AIPE). This complete study sheds light on the crucial role of structural isomerism of the triazole group, which has been unsuspected for a long time although it can govern the geometry and electronic properties of rhenium complexes. It is shown for the first time that grafting a non-coordinated π-conjugated fragment on the N(4) atom of a 1,2,4-triazole group can be of high value for the design of efficient light-emitting materials based on rhenium complexes.

A series of copper(I) pseudorotaxanes has been prepared from bis[2-(diphenylphosphino)phenyl] ether (POP) and macrocyclic phenanthroline ligands with different ring sizes (m30, m37, and m42). Variable-temperature studies carried out on the resulting [Cu(mXX)(POP)] + (mXX = m30, m37, and m42) derivatives have revealed a dynamic conformational equilibrium due to the folding of the macrocyclic ligand. The absorption and luminescence properties of the pseudorotaxanes have been investigated in CH 2 Cl 2 . They exhibit metal-to-ligand charge-transfer emission with photoluminescence quantum yields (PLQYs) in the range 20-30%. The smallest system [Cu(m30)(POP)] + shows minimal differences in spectral shape and position compared to its analogues, suggesting a slightly distorted coordination environment. PLQY is substantially enhanced in poly(methyl methacrylate) films (∼40-45%). The study of emission spectra and excited-state lifetimes in powder samples as a function of temperature (78-338 K) reveals thermally activated delayed fluorescence, with sizable differences in the singlet-triplet energy gap compared to the reference compound [Cu(dmp)(POP)] + (dmp = 2,9-dimethyl-1,10-phenanthroline) and within the pseudorotaxane series. The system with the largest ring ([Cu(m42)(POP)] + ) has been tested as emissive material in OLEDs and affords bright green devices with higher luminance and greater stability compared to [Cu(dmp)(POP)] + , which lacks the macrocyclic ring. This highlights the importance of structural factors in the stability of electroluminescent devices based on Cu(I) materials.

A rotaxane scaffold incorporating two dithiolane anchoring units for the modification of gold surfaces has been functionalized with multiple copies of a redox unit, namely ferrocene. Surface modification has been first assessed at the single molecule level by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) imaging, while tip enhanced Raman spectroscopy (TERS) provided the local vibrational signature of the ferrocenyl subunits of the rotaxanes grafted onto the gold surface. Finally, oxidation of the redox moieties within a rotaxane scaffold grafted onto gold microelectrodes has been investigated by ultrafast cyclic voltammetry. Intramolecular electron hopping is indeed extremely fast in this system. Moreover, the kinetics of charge injection depends on the molecular coverage due to the influence of intermolecular contacts on molecular motions., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A sophisticated photoactive molecular device has been prepared by combining recent concepts for the preparation of multifunctional nanomolecules (click chemistry on multifunctional scaffolds) with supramolecular chemistry (self-assembly to prepare rotaxanes). Specifically, a clickable [2]rotaxane scaffold incorporating a free-base porphyrin stopper has been prepared and functionalized with ten peripheral Zn(II)-porphyrin moieties. Electrochemical investigations of the final compound revealed a peculiar behavior resulting from the intramolecular coordination of the Zn(II) porphyrin moieties to 1,2,3-triazole units. Finally, steady state investigations of the compound combining Zn(II) and free-base porphyrin moieties have shown that this compound is a light-harvesting device capable of channeling the light energy from the peripheral Zn(II)-porphyrin subunits to the core by singlet-singlet energy transfer., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A pillar[5]arene-containing rotaxane building block bearing exchangeable stoppers has been prepared in multigram scale quantities with high yields from the reaction of 2,4-dinitrophenol (DNP) with the inclusion complex resulting from the association of dodecanedioyl chloride with 1,4-diethoxypillar[5]arene. Stopper exchange reactions have been achieved by treatment of the resulting DNP diester with various amines through an addition-elimination mechanism preventing the unthreading of the axle component during the reaction and thus preserving the [2]rotaxane structures. The resulting diamide [2]rotaxane derivatives have thus been obtained in good to excellent yields. Importantly, [2]rotaxanes difficult or impossible to prepare by direct introduction of the two stoppers in a single synthetic step are now easily available., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The dyads 1-3 made of an alkynylated Zn II -porphyrin and a bis-methanofullerene derivative connected through a copper-catalyzed azide-alkyne cycloaddition have been synthesized. The porphyrin and fullerene chromophores are separated through a bridge made of a bismethanofullerene tether linked to different spacers conjugated to the porphyrin moiety [i.e., m-phenylene (1), p-phenylene (2), di-p-phenylene-ethynylene (3)]. Compounds 1-3 exhibit relatively rigid structures with an interchromophoric separation of 1.7, 2.0, and 2.6 nm, respectively, and no face-to-face or direct through-bond conjugation. The photophysical properties of compounds 1-3 have been investigated in toluene and benzonitrile with steady-state and time-resolved techniques as well as model calculations on the Förster energy transfer. Excited-state interchromophoric electronic interactions are observed with a distinct solvent and distance dependence. The latter effect is evidenced in benzonitrile, where compounds 1 and 2 exhibit a photoinduced electron transfer in the Marcus-inverted region, with charge-separated (CS) states living for 0.44 and 0.59 μs, respectively, whereas compound 3 only undergoes energy transfer, as in apolar toluene. The quantum yield of the charge separation (φ CS ) of compounds 1 and 2 in benzonitrile is ≥0.75. It is therefore demonstrated that photoinduced energy and electron transfers in porphyrin-fullerene systems with long interchromophoric distances may efficiently occur also when the bridge does not provide a wire-like conjugation and proceed through the triplet states of the chromophoric moieties., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Pillar[5]arene derivatives bearing peripheral porphyrin subunits have been efficiently prepared from a deca-azide pillar[5]arene building block (17) and Zn II -porphyrin derivatives bearing a terminal alkyne function (9 and 16). For the resulting deca-Zn II -porphyrin arrays (18 and 20), variable temperature NMR studies revealed an intramolecular complexation of the peripheral Zn II -porphyrin moieties by 1,2,3-triazole subunits. As a result, the molecules adopt a folded conformation. This was further confirmed by UV/Vis spectroscopy and cyclic voltammetry. In addition, we have also demonstrated that the coordination-driven unfolding of 18 and 20 can be controlled by an external chemical stimulus. Specifically, addition of an imidazole derivative (22) to solution of 18 or 20 breaks the intramolecular coordination at the origin of the folding. The resulting molecular motions triggered by the addition of the imidazole ligand mimic the blooming of a flower., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Two new conjugated porphyrin-based systems (dimers 3 and 4) endowed with suitable crown ethers have been synthesized as receptors for a fullerene-ammonium salt derivative (1). Association constants in solution have been determined by UV-vis titration experiments in CH 2 Cl 2 at room temperature. The designed hosts are able to associate up to two fullerene-based guest molecules and present association constants as high as ∼5 × 10 8 M -1 . Calculation of the allosteric cooperative factor α for supramolecular complexes [3·1 2 ] and [4·1 2 ] showed a negative cooperative effect in both cases. The interactions accounting for the formation of the associates are based, first, on the complementary ammonium-crown ether interaction and, second, on the π-π interactions between the porphyrin rings and the C 60 moieties. Theoretical calculations have evidenced a significant decrease of the electron density in the porphyrin dimers 3 and 4 upon complexation of the first C 60 molecule, in good agreement with the negative cooperativity found in these systems. This negative effect is partially compensated by the stabilizing C 60 -C 60 interactions that take place in the more stable syn-disposition of [4·1 2 ].

A new concept is presented, namely the synthesis of dendrimers intrinsically composed in alternation of building blocks pertaining to two known families of dendrimers: phosphorhydrazone dendrimers and triazine-piperazine dendrimers. These mixed dendrimers with layered controlled architecture inherit their easy (31) P NMR characterization and their thermal stability from the phosphorhydrazone family, and their decreased solubility from the triazine-piperazine family. However, they have also their own and original characteristics. Both parent families are white powders, whereas the mixed dendrimers are yellow, orange, or red powders, depending on the generation. DFT calculations were carried out on model dendrons to understand these special color features. Remarkably, these dendrimers incorporating redox-active organic entities allow for the first time the monitoring of the growth of an organic dendrimer by electrochemistry while highlighting an even-odd generation behavior., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A fullerene ammonium derivative has been combined with different metalloporphyrin-crown ether receptors to generate very stable supramolecules. The combination of fullerene-porphyrin and ammonium-crown ether interactions leads to a strong chelate effect as evidenced by a high effective molarity (3.16 M). The different parameters influencing the stability of the supramolecular ensembles, in particular the nature of the metal in the porphyrin moiety, have been rationalized with the help of theoretical calculations thus providing new insights into fullerene-porphyrin interactions., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Heteroleptic copper(I) complexes have been prepared from a macrocyclic ligand incorporating a 2,9-diphenyl-1,10-phenanthroline subunit (M30) and two bis-phosphines, namely bis[(2-diphenylphosphino)phenyl] ether (POP) and 1,3-bis(diphenylphosphino)propane (dppp). In both cases, the diphenylphosphino moieties of the PP ligand are too bulky to pass through the 30-membered ring of M30 during the coordination process, hence the formation of C2v-symmetrical pseudo-rotaxanes is prevented. When POP is used, X-ray crystal structure analysis shows the formation of a highly distorted [Cu(M30)(POP)](+) complex in which the POP ligand is only partially threaded through the M30 unit. This compound is poorly stable as the Cu(I) cation is not in a favorable coordination environment due to steric constraints. By contrast, in the case of dppp, the bis-phosphine ligand undergoes both steric and topological constraints and adopts a nonchelating coordination mode to generate [Cu2(M30)2(μ-dppp)](BF4)2. This compound exhibits metal-to-ligand charge transfer (MLCT) emission characterized by a very large Stokes' shift (≈200 nm) that is not attributed to a dramatic structural distortion between the ground and the emitting states but to very weak MLCT absorption transitions at longer wavelengths. Accordingly, [Cu2(M30)2(μ-dppp)](BF4)2 shows unusually high luminescence quantum yields for Cu(I) complexes, both in solution and in the solid state (0.5 and 7 %, respectively)., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The heteroleptic coordination scenario of silver(I) with various phenanthroline ligands (NN) and different bis-phosphine (PP) derivatives has been investigated. In addition to the X-ray crystal structural characterization of the resulting mixed ligand Ag(I) complexes, detailed NMR studies have been performed to disclose the behavior of the prepared silver(I) complexes in solution. The results obtained with silver(I) have been also systematically related to the one obtained for copper(I) with the same combination of PP and NN ligands. Starting from an equimolar mixture of AgBF4, bis[(2-diphenylphosphino)phenyl] ether (POP), and 1,10-phenanthroline (phen), the mononuclear complex [Ag(POP)(phen)](+) has been obtained as the tetrafluoroborate salt. By following the same experimental procedure starting from bis(diphenylphosphino)methane (dppm) or 1,3-bis(diphenylphosphino)propane (dppp) as the PP ligand, dinuclear complexes with two bridging PP ligands, i.e., [Ag2(NN)2(μ-dppm)2](2+) and [Ag2(NN)2(μ-dppp)2](2+) with NN = phen or Bphen (bathophenanthroline), have been isolated as the tetrafluoroborate salts. Surprisingly, by using an equimolar ratio of AgBF4, phen or Bphen, and 1,2-bis(diphenyl-phosphino)ethane (dppe), the corresponding monobridged diphosphine dinuclear complexes [Ag2(NN)2(μ-dppe)](2+) have been obtained as the tetrafluoroborate salts. These compounds have been also prepared in excellent yield by using a more appropriate 2:1:2 (phen:dppe:Ag) stoichiometry. These results prompted us to also perform the reactions with dppm and dppp using a 1:2:2 (PP:NN:Ag) stoichiometry. Under these conditions, [Ag2(NN)2(μ-dppm)](BF4)2 (NN = phen or Bphen) and [Ag2(NN)2(μ-dppp)](BF4)2 (NN = phen or Bphen) have been obtained upon crystallization. When compared to their copper(I) analogues, the complexation scenario becomes more complex with silver(I) as the system tolerates also coordinatively frustrated metal ligand assemblies, i.e., with a trigonal coordination geometry. Depending on the stoichiometry or on the nature of the PP partner, silver(I) shows an adaptive capability leading to various complexes with different coordination geometries and composition. However, as in the case of copper(I), their solution behavior is highly dependent on the relative thermodynamic stability of the various possible complexes. In most of the cases, a single Ag(I) complex is observed in solution and the NMR data are in a perfect agreement with their solid state structures. The dppp-containing complexes are the only notable exception; both [Ag2(NN)2(μ-dppp)2](BF4)2 and [Ag2(NN)2(μ-dppp)](BF4)2 are stable in the solid state but a dynamic mixture is observed as soon as these compounds are dissolved. Finally, whereas both dppe and dppp are chelating ligands for copper(I), it is not the case anymore with silver(I) for which a destabilization of species with chelating dppe and dppp ligands is clearly suggested by our results.

Preparation of [Cu(NN)(PP)](+) derivatives has been systematically investigated starting from two libraries of phenanthroline (NN) derivatives and bis-phosphine (PP) ligands, namely, (A) 1,10-phenanthroline (phen), neocuproine (2,9-dimethyl-1,10-phenanthroline, dmp), bathophenanthroline (4,7-diphenyl-1,10-phenanthroline, Bphen), 2,9-diphenethyl-1,10-phenanthroline (dpep), and 2,9-diphenyl-1,10-phenanthroline (dpp); (B) bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)benzene (dppb), 1,1'-bis(diphenylphosphino)ferrocene (dppFc), and bis[(2-diphenylphosphino)phenyl] ether (POP). Whatever the bis-phosphine ligand, stable heteroleptic [Cu(NN)(PP)](+) complexes are obtained from the 2,9-unsubstituted-1,10-phenanthroline ligands (phen and Bphen). By contrast, heteroleptic complexes obtained from dmp and dpep are stable in the solid state, but a dynamic ligand exchange reaction is systematically observed in solution, and the homoleptic/heteroleptic ratio is highly dependent on the bis-phosphine ligand. Detailed analysis revealed that the dynamic equilibrium resulting from ligand exchange reactions is mainly influenced by the relative thermodynamic stability of the different possible complexes. Finally, in the case of dpp, only homoleptic complexes were obtained whatever the bis-phosphine ligand. Obviously, steric effects resulting from the presence of the bulky phenyl rings on the dpp ligand destabilize the heteroleptic [Cu(NN)(PP)](+) complexes. In addition to the remarkable thermodynamic stability of [Cu(dpp)2]BF4, this negative steric effect drives the dynamic complexation scenario toward almost exclusive formation of homoleptic [Cu(NN)2](+) and [Cu(PP)2](+) complexes. This work provides the definitive rationalization of the stability of [Cu(NN)(PP)](+) complexes, marking the way for future developments in this field.

Treatment of 2-diphenylphosphino-6-methylpyridine (dpPyMe) with Cu(CH(3)CN)(4)BF(4) afforded the stable dinuclear Cu(I) complex [Cu(2)(μ-dpPyMe)(3)(CH(3)CN)](BF(4))(2). This compound is a weak emitter in solution, however a remarkably high emission quantum yield (46%) has been found in a rigid matrix at room temperature.

Diethylamino-substituted oligophenylenevinylene (OPV) building blocks have been prepared and used for the synthesis of two [60]fullerene-OPV dyads, F-D1 and F-D2, which exhibit different conjugation length of the OPV fragments. The electrochemical properties of these acceptor-donor dyads have been studied by cyclic voltammetry. The first reduction is always assigned to the fullerene moiety and the first oxidation centered on the diethylaniline groups of the OPV rods, thus making these systems suitable candidates for photoinduced electron transfer. Both the OPV and the fullerene-centered fluorescence bands are quenched in toluene and benzonitrile, which suggests the occurrence of photoinduced electron transfer from the amino-substituted OPVs to the carbon sphere in the dyads in both solvents. By means of bimolecular quenching experiments, transient absorption spectral fingerprints of the radical cationic species are detected in the visible (670 nm) and near-IR (1300-1500 nm) regions, along with the much weaker fullerene anion band at lambda(max)=1030 nm. Definitive evidence for photoinduced electron transfer in F-D1 and F-D2 comes from transient absorption measurements. A charge-separated state is formed within 100 ps and decays in less than 5 ns.

Heteroleptic copper(I) complexes CuPOP-F and CuFc-F have been prepared from a fullerene-substituted phenanthroline ligand and bis[2-(diphenylphosphino)phenyl] ether (POP) and 1,1'-bis(diphenylphosphino)ferrocene (dppFc), respectively. Electrochemical studies indicate that some ground-state electronic interaction between the fullerene subunit and the metal-complexed moiety are present in both CuPOP-F and CuFc-F. Their photophysical properties have been investigated by steady state and time-resolved UV-vis-NIR luminescence spectroscopy and nanosecond laser flash photolysis in a CH2Cl2 solution and compared to those of the corresponding model copper(I) complexes CuPOP and CuFc and of the fullerene model compound F. Selective excitation of the methanofullerene moiety in CuPOP-F results in regular deactivation of the lowest singlet and triplet states, indicating no intercomponent interactions. Conversely, excitation of the copper(I)-complexed unit (405 nm, 40% selectivity) shows that the strongly luminescent triplet metal-to-ligand charge-transfer ((3)MLCT) excited state located at 2.40 eV is quenched by the carbon sphere with a rate constant of 1.6 x 10(8) s(-1). Details on the mechanism of photodynamic processes in CuPOP-F via transient absorption are hampered by the rather unfavorable partition of light excitation between the two chromophores. By determination of the yield of formation of the lowest fullerene triplet level through sensitized singlet oxygen luminescence in the NIR region, it is shown that the final sink of photoinduced processes is always the fullerene triplet. This can be populated via a two-step charge-separation charge-recombination process and a less favored (3)MLCT --> (3)C60 triplet-triplet energy-transfer pathway. In CuFc-F, both of the photoexcited copper(I)-complexed and fullerene moieties are quenched by the presence of the ferrocene unit, most likely via ultrafast energy transfer.

A Th-symmetrical C60 hexakis-adduct bearing 12 peripheral azide groups has been prepared and used to produce functionalized derivatives by the copper mediated Huisgen 1,3-dipolar cycloaddition of azides and alkynes.

Mixtures of an appropriate carboxylic acid and n-butylstannoic acid constitute modular gelation systems, in which the formation of a well-defined 'tin-drum' nanocluster subsequently underpins the hierarchical assembly of nanostructured fibres, which form self-supporting gel-phase networks in organic solvents.

The strength of the electronic interactions between the two redox moieties in fullerene-substituted mixed-valence bis(ferrocenylethynyl)ethene derivatives is modulated by the through-space intramolecular electronic interactions of C(60) with the bridging conjugated system.

The first system containing a luminescent Ir(m) cyclometallated species and a functionalized C60 unit has been prepared; triplet-triplet energy transfer from the Ir-based MLCT state to the C60 triplet state occurs, leading to phosphorescence (lifetime, 4.8 ms) of the derivatized-C60 at 77 K.

Homo- and heteroleptic copper(I) complexes obtained from various chelating bis-phosphine ligands and Cu(CH3CN)4BF4 have been used for the preparation of light emitting devices.