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Donor–acceptor (D–A) hybrid heterostructures are an emerging class of hybrid complexes with potential applications in current optoelectronic technologies. To achieve high photoinduced charge-carrier generation and separation in a heterostructure, a common strategy is the fabrication of continuous or bicontinuous structures by the crystallization of semiconductive donor and acceptor tectons at the molecular level. So far, only a few such heterostructures have been fabricated, most of which involve unstable and narrow band gap metal halides. In this paper, we extended these unique hybrid heterostructures to continuous alkaline-earth metal oxide clusters. The combination of the naphthalene diimide (NDI) tecton bearing four carboxylates at two extremities with Ca2+ (or Sr2+) cations led to two isostructural D–A hybrid heterostructures with infinite 1-D carbon-doped alkaline-earth metal oxide clusters and X-aggregated NDI dimers as electron donors and acceptors, respectively. Due to the different metal cations in inorganic clusters, they exhibited diametrically opposite photochromic sensitivities and photocatalytic activities. To better rationalize them, a plausible photoinduced electron transfer process for the D–A hybrid heterostructures with photoactive acceptors has been developed. [ABSTRACT FROM AUTHOR]

Four mononuclear Cu(i)–halide complexes containing phosphines and pyridine ligands with strong electron donor substituents, [CuCl(PPh3)2(4-NMe2py)] (1), [CuI(PPh3)2(4-NH2py)] (2), [CuI(POP)(4-NH2py)] (3), and [CuI(POP)(4-NMe2py)]·0.5(Et2O) (4), (PPh3 = triphenylphosphine, 4-NMe2py = 4-(dimethylamino)pyridine, POP = bis[(2-diphenyl-phosphino)phenyl]ether, 4-NH2py = 4-aminopyridine, Et2O = diethyl ether) were synthesized and studied with regard to their structural, photophysical properties and theoretical calculations. The complexes exhibit pure blue thermally activated delayed fluorescence (λmax = 442 (1), 436 (2), 464 (3), and 448 nm (4)) in crystalline at room temperature. Emission lifetime analyses and density functional theory (DFT) calculations show that the blue-light emission at room temperature is the singlet (metal + halide)-to-ligand charge transfer state, (1(M + X)LCT), while that at 77 K is the state of 3(M + X)LCT transition character, owing to the small singlet–triplet energy gaps (ΔE = 660–1680 cm−1). X-ray diffraction structure analysis, photophysical studies and theoretical calculations suggest that the much larger torsion angle between the N-heterocyclic rings and N–Cu–X planes of complex 3 than that of 1, 2 and 4 might causes the bathochromic shift of luminescence, although these complexes containing similar heterocycle ligands. [ABSTRACT FROM AUTHOR]