The series of chelating phosphine ligands, which contain bidentate P² (bis[(2-diphenylphosphino)phenyl] ether, DPEphos; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, Xantphos; 1,2-bis(diphenylphosphino)benzene, dppb), tridentate P³ (bis(2-diphenylphosphinophenyl)phenylphosphine), and tetradentate P⁴ (tris(2-diphenylphosphino)phenylphosphine) ligands, was used for the preparation of the corresponding dinuclear [M(μ₂-SCN)P²]₂ (M = Cu, 1, 3, 5; M = Ag, 2, 4, 6) and mononuclear [CuNCS(P³/P⁴)] (7, 9) and [AgSCN(P³/P⁴)] (8, 10) complexes. The reactions of P⁴ with silver salts in a 1:2 molar ratio produce tetranuclear clusters [Ag₂(μ₃-SCN)(t-SCN)(P⁴)]₂ (11) and [Ag₂(μ₃-SCN)(P⁴)]₂²⁺ (12). Complexes 7–11 bearing terminally coordinated SCN ligands were efficiently converted into derivatives 13–17 with the weakly coordinating ^–SCN:B(C₆F₅)₃ isothiocyanatoborate ligand. Compounds 1 and 5–17 exhibit thermally activated delayed fluorescence (TADF) behavior in the solid state. The excited states of thiocyanate species are dominated by the ligand to ligand SCN → π(phosphine) charge transfer transitions mixed with a variable contribution of MLCT. The boronation of SCN groups changes the nature of both the S₁ and T₁ states to (L + M)LCT d,p(M, P) → π(phosphine). The localization of the excited states on the aromatic systems of the phosphine ligands determines a wide range of luminescence energies achieved for the title complexes (λ_em varies from 448 nm for 1 to 630 nm for 10c). The emission of compounds 10 and 15, based on the P⁴ ligand, strongly depends on the solid-state packing (λ_em = 505 and 625 nm for two crystalline forms of 15), which affects structural reorganizations accompanying the formation of electronically excited states.

A series of diimine ligands has been designed on the basis of 2-pyridyl-1H-phenanthro[9,10-d]imidazole (L1, L2). Coupling the basic motif of L1 with anthracene-containing fragments affords the bichromophore compounds L3–L5, of which L4 and L5 adopt a donor–acceptor architecture. The latter allows intramolecular charge transfer with intense absorption bands in the visible spectrum (lowest λ_abs 464 nm (ε = 1.2 × 10⁴ M^–1 cm^–1) and 490 nm (ε = 5.2 × 10⁴ M^–1 cm^–1) in CH₂Cl₂ for L4 and L5, respectively). L1–L5 show strong fluorescence in a fluid medium (Φ_em = 22–92%, λ_em 370–602 nm in CH₂Cl₂); discernible emission solvatochromism is observed for L4 and L5. In addition, the presence of pyridyl (L1–L5) and dimethylaminophenyl (L5) groups enables reversible alteration of their optical properties by means of protonation. Ligands L1–L5 were used to synthesize the corresponding [Re(CO)₃X(diimine)] (X = Cl, 1–5; X = CN, 1-CN) complexes. 1 and 2 exhibit unusual dual emission of singlet and triplet parentage, which originate from independently populated ¹ππ* and ³MLCT excited states. In contrast to the majority of the reported Re(I) carbonyl luminophores, complexes 3–5 display moderately intense ligand-based fluorescence from an anthracene-containing secondary chromophore and complete quenching of emission from the ³MLCT state presumably due to the triplet–triplet energy transfer (³MLCT → ³ILCT).

Crystalline diphosphonium iodides [MeR₂P‐spacer‐R₂Me]I with phenylene (1, 2), naphthalene (3, 4), biphenyl (5) and anthracene (6) as aromatic spacers, are photoemissive under ambient conditions. The emission colors (λ_em values from 550 to 880 nm) and intensities (Φ_em reaching 0.75) are defined by the composition and substitution geometry of the central conjugated chromophore motif, and the anion‐π interactions. Time‐resolved and variable‐temperature luminescence studies suggest phosphorescence for all the titled compounds, which demonstrate observed lifetimes of 0.46–92.23 μs at 297 K. Radiative rate constants k_r as high as 2.8×10⁵ s⁻¹ deduced for salts 1–3 were assigned to strong spin‐orbit coupling enhanced by an external heavy atom effect arising from the anion‐π charge‐transfer character of the triplet excited state. These rates of anomalously fast metal‐free phosphorescence are comparable to those of transition metal complexes and organic luminophores that utilize triplet excitons via a thermally activated delayed fluorescence mechanism, making such ionic luminophores a new paradigm for the design of photofunctional and responsive molecular materials.

Strongly blue fluorescent 1-phenyl-2-(pyridin-2-yl)-1H-phenanthro[9,10-d]imidazole (L1) is a facile block for the construction of multichromophore organic molecules, and simultaneously serves as a chelating diimine ligand. The coordination of L1 to zinc halides enhances the intraligand charge transfer and decreases the emission energy. For the iodide derivative, intra- and intermolecular heavy atom effects lead to a dual singlet–triplet emission with a temperature-dependent ratio of fluorescence and phosphorescence bands in the crystalline state. Decoration of the anthracene core with pyridyl-phenanthroimidazole units (L2 and L3) changes the localization of the lowest energy electronic transitions to the former polyaromatic motif. The solid-state photophysical characteristics of L2 and L3-based compounds strongly depend on the intermolecular interactions between the constituting π-systems (phenanthrene and anthracene), which are perturbed by the ZnX₂ coordinated fragments. Modulation of π-stacking contacts in these molecular materials containing L2 and L3 chromophores forms a basis for dynamic optical properties, responsive to mechanical, thermal, or chemical stimuli.

Linking two cyclometalated Pt( ii ) fragments via cyanido bridge improves the luminescence and dramatically enhances the aggregation ability resulting in distinct sensitivity to the properties of the surrounding medium.