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Abstract: Phenanthroline derivative, 4,5-diazafluoren-9-one(dafone), was introduced into lead iodine hybrid to synthesize a new hybrid [Pb2I4(dafone)2] n (1), in which each lead atom adopts a distorted octahedral coordination and presents a one-dimensional polymer by edge-sharing mode. Due to the presence of O acceptor in dafone, C–H⋯O hydrogen bonds can be observed and contribute to the formation of 2-D layer. Experimental and theoretical optical property investigation indicate that 1 possesses semiconductor property. Specially, DFT calculation suggests that 1 displays a reduced band gap (1.36eV), which is assigned to a more dispersed LUMO band compared with [Pb2I4(phen)2] n and [Pb2I4(bipy)2] n . [ABSTRACT FROM AUTHOR]

Abstract: Dark-red block-shaped crystals of the ionic compound (ipq)4[(Cu2I6)·2I2] (1) (ipq+ = N-(isopentyl)-quinolinium) were obtained by the reaction of ibq·I, CuI with I2 in polar solvent DMF. Compound 1 crystallizes in triclinic system [space group Z =2, a =10.4236(8)Å, b =12.1950(9)Å, c =15.6214(10)Å, α =95.879(2)°, β =102.174(2)° and γ =113.757(2)°]. As indicated by structural analysis, 1 is constituted by ipq+ cations, [Cu2I6]4− anions and molecular iodine [d I−I =2.8499(5)Å]. In 1, dimer Cu2I6 4− anion is composed by two edge-sharing CuI4 tetrahedra. Cu2I6 4− anions interact with I2 via strong I⋯I interaction to give [(Cu2I6)·2I2]4− clusters. Furthermore, electrostatic interactions between organic cations and inorganic clusters could be observed and contribute to the crystal packing. Finally, quantum chemistry calculation with DFT method was carried out to reveal the electronic structure of 1. [Copyright &y& Elsevier]

Through the incorporation of Cu(II) ions as additional connecting nodes to form heterometallic uranyl-organic frameworks with rigid ligands, we have successfully synthesized three extended complexes with varying dimensions. Notably, complex 1 features a robust 3D cds net structure and demonstrates exceptional thermal stability above 250 °C. [Display omitted] By introducing Cu(II) ions as additional connecting nodes to construct stable heterometallic uranyl-organic frameworks (UOFs) with thiophene-2,5-dicarboxylic acid (H 2 TDC) and N -donor auxiliary ligands, three new uranyl complexes, namely, [Cu(phen)(UO 2)(TDC) 2 ] (1), [Cu(phen-NO 2) 2 (UO 2)(TDC) 2 ]·3H 2 O (2), and [Cu(phen-NH 2)(H 2 O) 2 (UO 2)(TDC) 2 ]·4H 2 O (3) (phen = 1,10-phenanthroline) have been successfully synthesized by hydrothermal reaction. Complex 1 exhibits a rare three-dimensional (3D) network structure of cds topology connected by UO 2 , Cu(phen), and TDC units. Both complexes 2 and 3 feature similar one-dimensional chain structures based on UO 2 , TDC, Cu(Phen-NO 2) 2 and UO 2 , TDC, Cu(phen-NH 2)(H 2 O) 2 respectively. The N -donor auxiliary ligands play a key role in determining their structural dimensionalities and bandgaps formation. Among the three uranyl complexes, phen with a smaller size than its derivatives, phen-NO 2 and phen-NH 2 , was found to be favorable for constructing 3D UOFs. Moreover, complexes with both phen-NO 2 and phen-NH 2 showed varying degrees of redshift on optical spectra. The UV–Visible diffuse-reflectance spectra, analyzed with Tauc's fitting in considering Urbach tailing, revealed an indirect bandgap of 2.94 eV, an indirect bandgap of 2.67 eV, and a direct bandgap of 2.45 eV for 1 , 2 and 3 , respectively. Moreover, thermogravimetric analyses indicate that 3D anhydrous uranyl complex 1 possessed a robust structure and excellent thermal stability above 250 ℃. [ABSTRACT FROM AUTHOR]

The combination of N , N ′-dipyridyl-tetrachloroperylene diimide (4Cl-DPPDI) buliding blocks with lead iodides in the presence of hydrogen iodides led to a novel D-A hybrid heterostructure with segregated iodoplumbate anions and 2-D H-bonded 4Cl-DPPDI networks as electron donors and acceptors. Due to the compact anion-π interactions as well as small energy gaps between the donors and acceptors, persistent and stable radical anions are generated in such a unique complex triggered by natural-light irradiation, which thus exhibits a panchromatic absorption. Induced by the compact anion-π interactions and small energy gaps between the donor and acceptor components, persistent radical anions are photogenerated in a novel D-A hybrid heterostructure, which thus exhibits a panchromatic absorption. Image 1 • A novel D-A hybrid heterostructure composed of perylene diimide dyes and iodoplumbate anions have been synthesized. • In the structure, the iodoplumbate anions and perylene diimide networks acted as electron donors and acceptors, respectively. • The donor and acceptor components in the heterostructure are interconnected through the anion-π interactions. • Due to the compact connections, persistent and stable radical anions are triggered by natural-light irradiation. • The generation mechanism of these persistent and stable radical anions was studied through theoretical calculation. [ABSTRACT FROM AUTHOR]