Silver(I)−Thiophene π Interaction in the Assembly of Coordination Networks with the Supramolecular Synthons R−C⋮C⊃Ag<i>_n</i> (R = 2- or 3-thienyl; <i>n</i> = 4)^†

Silver−thiophene π interactions in two bonding modes, namely, η2-(CC) and κ-(C,S), have been observed for the first time in crystalline silver(I) complexes (C4H3S-2)C⋮CAg·4AgCF3CO2 (1), 2[(C4H3S-2)C⋮CAg]·8AgCF3CO2·CH3CN (2), and (C4H3S-3)C⋮CAg·4AgCF3CO2 (4), bearing thiophene ligands with an ethynide substituent at the 2- or 3-position. Introduction of an additional betaine component in 3[(C4H3S-2)C⋮CAg]·8AgCF3CO2·Me3N+CH2CO2-·4.5H2O (3) and replacement of trifluoroacetate by pentafluoropropionate in (C4H3S-3)C⋮CAg·5AgC2F5CO2·4H2O (5) were found to interrupt these silver−thiophene π interactions and instead form an infinite π−π-stacked silver chain and a π−π-stacking-stabilized Ag8 aggregate, respectively. The establishment of a new kind of silver−ethynide supramolecular synthon, R−C⋮C⊃Agn (R = 2-, 3-thienyl; n = 4), highlights the potential of building metal−organic frameworks utilizing the π-coordination capacity of a heterocyclic ring

Silver(I)−Thiophene π Interaction in the Assembly of Coordination Networks with the Supramolecular Synthons R−C⋮C⊃Ag<i>_n</i> (R = 2- or 3-thienyl; <i>n</i> = 4)^†

Silver−thiophene π interactions in two bonding modes, namely, η2-(CC) and κ-(C,S), have been observed for the first time in crystalline silver(I) complexes (C4H3S-2)C⋮CAg·4AgCF3CO2 (1), 2[(C4H3S-2)C⋮CAg]·8AgCF3CO2·CH3CN (2), and (C4H3S-3)C⋮CAg·4AgCF3CO2 (4), bearing thiophene ligands with an ethynide substituent at the 2- or 3-position. Introduction of an additional betaine component in 3[(C4H3S-2)C⋮CAg]·8AgCF3CO2·Me3N+CH2CO2-·4.5H2O (3) and replacement of trifluoroacetate by pentafluoropropionate in (C4H3S-3)C⋮CAg·5AgC2F5CO2·4H2O (5) were found to interrupt these silver−thiophene π interactions and instead form an infinite π−π-stacked silver chain and a π−π-stacking-stabilized Ag8 aggregate, respectively. The establishment of a new kind of silver−ethynide supramolecular synthon, R−C⋮C⊃Agn (R = 2-, 3-thienyl; n = 4), highlights the potential of building metal−organic frameworks utilizing the π-coordination capacity of a heterocyclic ring

Hydrogen-Bonded Supramolecular Architecture by Solvomorphism of Hexahydroxytriptindane: From a Rosette Network to a Rod Structure

Triptindane derivative L bearing three sets of para-dihydroxyl groups in C3 arrangement was synthesized and characterized by NMR spectroscopy, mass spectroscopy, and X-ray crystallography. Crystallization of L in water or various organic solvents yielded diversified three-dimensional (3D) supramolecular architectures, including a hexagonal rosette network, a C4-symmetric channel, and corrugated layers. These solvomorphs are consolidated by intermolecular O–H···O hydrogen bonds involving exo- and endo-hydroxyl groups of triptindane L and the solvent molecules. In particular, the molecular arrangement of the exo- and endo-hydroxyl groups of L facilitates the formation of the three-dimensional hexagonal rosette network

Solution Study of a Structurally Characterized Monoalkoxo-Bound Monooxo-Vanadium(V) Complex: Spontaneous Generation of the Corresponding Oxobridged Divanadium(V,V) Complex and its Electroreduction to a Mixed-Valence Species in Solution

An interesting transformation of a structurally characterized monooxoalkoxovanadium(V) complex [VO(OEt)L] (LH2 = a dibasic tridentate ONO donor ligand) in solution leading to the formation of the corresponding monooxobridged divanadium(V,V) complex (VOL)2O is reported. This binuclear species in solution is adequately characterized by elemental analysis, measurement of conductance (in solution), various spectroscopic (UV−vis, IR, NMR, and mass spectrometry) techiniques and by cyclic voltammetry. The corresponding mixed-valence vanadium(IV,V) species has been generated in CH3CN solution by controlled potential electrolysis of (VOL)2O. This mixed-valence species is identified and studied by EPR technique (at room temperature and at liquid nitrogen temperature) and also by UV−vis spectroscopy. This study may be regarded as a general method of obtaining monooxo-bridged binuclear vanadium(V,V) species from the corresponding mononuclear monooxoalkoxovanadium(V) complexes of some selected dibasic tridentate ONO chelating ligands, which can be utilized as the precursor of monooxobridged divanadium(IV,V) mixed-valence species in solution obtainable by controlled potential electrolysis

Solution Study of a Structurally Characterized Monoalkoxo-Bound Monooxo-Vanadium(V) Complex: Spontaneous Generation of the Corresponding Oxobridged Divanadium(V,V) Complex and its Electroreduction to a Mixed-Valence Species in Solution

An interesting transformation of a structurally characterized monooxoalkoxovanadium(V) complex [VO(OEt)L] (LH2 = a dibasic tridentate ONO donor ligand) in solution leading to the formation of the corresponding monooxobridged divanadium(V,V) complex (VOL)2O is reported. This binuclear species in solution is adequately characterized by elemental analysis, measurement of conductance (in solution), various spectroscopic (UV−vis, IR, NMR, and mass spectrometry) techiniques and by cyclic voltammetry. The corresponding mixed-valence vanadium(IV,V) species has been generated in CH3CN solution by controlled potential electrolysis of (VOL)2O. This mixed-valence species is identified and studied by EPR technique (at room temperature and at liquid nitrogen temperature) and also by UV−vis spectroscopy. This study may be regarded as a general method of obtaining monooxo-bridged binuclear vanadium(V,V) species from the corresponding mononuclear monooxoalkoxovanadium(V) complexes of some selected dibasic tridentate ONO chelating ligands, which can be utilized as the precursor of monooxobridged divanadium(IV,V) mixed-valence species in solution obtainable by controlled potential electrolysis

Formation of Germenes from Bis(germavinylidene)

A series of germenes have been synthesized from the bis(germavinylidene) [(Me3SiNPPh2)2CGe→GeC(PPh2NSiMe3)2] (1). The reaction of 1 with 2,2,6,6-tetramethylpiperidine N-oxide afforded [(Me3SiNPPh2)2CGe(ONCMe2C3H6CMe2)2] (2). Germavinylidene, the dissociation derivative of 1, underwent [1 + 4] cycloaddition with azobenzene, followed by a 1,3-H shift to give [(Me3SiNPPh2)2CGe(o-C6H4NHNPh)] (3). Treatment of 1 with benzil afforded the [1 + 4] cycloaddition compound [(Me3SiNPPh2)2CGe{O(Ph)CC(Ph)O}] (4). The results showed that the germavinylidene moiety dissociated from 1 acts as a synthon for the preparation of various germenes by addition to the germanium(II) center. The molecular structures of 2−4 have been determined

Solution Study of a Structurally Characterized Monoalkoxo-Bound Monooxo-Vanadium(V) Complex: Spontaneous Generation of the Corresponding Oxobridged Divanadium(V,V) Complex and its Electroreduction to a Mixed-Valence Species in Solution

An interesting transformation of a structurally characterized monooxoalkoxovanadium(V) complex [VO(OEt)L] (LH2 = a dibasic tridentate ONO donor ligand) in solution leading to the formation of the corresponding monooxobridged divanadium(V,V) complex (VOL)2O is reported. This binuclear species in solution is adequately characterized by elemental analysis, measurement of conductance (in solution), various spectroscopic (UV−vis, IR, NMR, and mass spectrometry) techiniques and by cyclic voltammetry. The corresponding mixed-valence vanadium(IV,V) species has been generated in CH3CN solution by controlled potential electrolysis of (VOL)2O. This mixed-valence species is identified and studied by EPR technique (at room temperature and at liquid nitrogen temperature) and also by UV−vis spectroscopy. This study may be regarded as a general method of obtaining monooxo-bridged binuclear vanadium(V,V) species from the corresponding mononuclear monooxoalkoxovanadium(V) complexes of some selected dibasic tridentate ONO chelating ligands, which can be utilized as the precursor of monooxobridged divanadium(IV,V) mixed-valence species in solution obtainable by controlled potential electrolysis

Full-Color Tunable Circularly Polarized Luminescence Induced by the Crystal Defect from the Co-assembly of Chiral Silver(I) Clusters and Dyes

Four pairs of defective crystals exhibiting full-color emission and circularly polarized luminescence (CPL) with high luminescence dissymmetry factor (glum) values (∼3 × 10–3) were successfully obtained by doping dye molecules into the chiral crystalline metal cluster-based matrixes. The dye molecules function as defect inducers and confer fluorescence on the crystals. Studies reveal that electrostatic interactions provide the main impetus in generating defective crystals, and the restricted effect of chiral space and the weak interactions in defect crystal enable the efficient chiral transfer from the intrinsically chiral host silver­(I) clusters to achiral luminescent dopants and finally induce them to emit bright CPL. This defect engineering strategy opens a new way to versatile functions for crystalline cluster-based materials

Modular Cocrystallization of Customized Carboranylthiolate-Protected Copper Nanoclusters via Host–Guest Interactions

Cocrystals containing distinct atom-precise metal nanoclusters (NCs) provide an opportunity to elucidate the crystallization process, architectural complexity, and newly emerging properties of condensed-state metal NC-assembled materials. However, the controllable preparation of such cocrystals is still challenging. Herein, we present a modular strategy to cocrystallize two customized carboranylthiolate-protected copper NCs, Cu14(C2B10H10S2)6(CH3CN)6 (Cu14) and Cu16(C2B10H10S2)8 (Cu16), which adopt matched surface patterns by host–guest chemistry. The Cu14·Cu16 cocrystals show integrated UV–vis adsorption and dual emission stemming from the Cu14 and Cu16 NCs. Moreover, the component NCs are selectively doped by gold atoms, which is a promising way to incorporate diverse properties of metal cluster-based cocrystals. This work not only provides a copper NC-based cocrystal for a profound study on a condensed-state copper nanomaterial but also develops a modular strategy for the cocrystallization of metal NCs

Modular Cocrystallization of Customized Carboranylthiolate-Protected Copper Nanoclusters via Host–Guest Interactions

Cocrystals containing distinct atom-precise metal nanoclusters (NCs) provide an opportunity to elucidate the crystallization process, architectural complexity, and newly emerging properties of condensed-state metal NC-assembled materials. However, the controllable preparation of such cocrystals is still challenging. Herein, we present a modular strategy to cocrystallize two customized carboranylthiolate-protected copper NCs, Cu14(C2B10H10S2)6(CH3CN)6 (Cu14) and Cu16(C2B10H10S2)8 (Cu16), which adopt matched surface patterns by host–guest chemistry. The Cu14·Cu16 cocrystals show integrated UV–vis adsorption and dual emission stemming from the Cu14 and Cu16 NCs. Moreover, the component NCs are selectively doped by gold atoms, which is a promising way to incorporate diverse properties of metal cluster-based cocrystals. This work not only provides a copper NC-based cocrystal for a profound study on a condensed-state copper nanomaterial but also develops a modular strategy for the cocrystallization of metal NCs