Photoinduced Isomerization-Driven Structural Transformation Between Decanuclear and Octadecanuclear Gold(I) Sulfido Clusters

Upon photoirradiation, isomerization of the ligands, 1,2-bis­(diphenylphosphino)­ethene (dppee) from the cis to the trans form in polynuclear gold­(I) sulfido clusters, led to the structural transformation of the decagold­(I) cluster to the octadecagold­(I) cluster. Both polynuclear μ₃-sulfido gold­(I) clusters have been fully characterized by NMR, mass spectrometry, elemental analysis, and single crystal X-ray diffraction analysis. The transformation process could be readily detected and monitored by UV–vis absorption, emission, and ³¹P NMR spectroscopy in solution. Supported and driven by Au­(I)···Au­(I) bonding interactions, the nuclearity and symmetry of these clusters were largely different from each other, resulting in completely distinct photophysical features

Self-Assembly of [M₈L₄] and [M₄L₂] Fluorescent Metallomacrocycles with Carbazole-Based Dipyrazole Ligands

Fluorescent carbazole-based dipyrazole ligands (<b>H</b>_<b>2</b><b>L</b>^{<b>1</b>–<b>4</b>}) were employed to coordinate with dipalladium corners ([(phen)₂Pd₂(NO₃)₂]­(NO₃)₂, [(dmbpy)₂Pd₂(NO₃)₂]­(NO₃)₂, or [(15-crown-5-phen)₂Pd₂(NO₃)₂]­(NO₃)₂, where phen = 1,10-phenanthroline and dmbpy = 4,4′-dimethyl-2,2′-bipyridine, in aqueous solution to afford a series of positively charged [M₈L₄]⁸⁺ or [M₄L₂]⁴⁺ multimetallomacrocycles with remarkable water solubility. Their structures were characterized by ¹H NMR spectroscopy, electrospray ionization mass spectrometry, and elemental analysis and in the cases of <b>1</b>·8BF₄^– ([(phen)₈Pd₈<b>L</b>^<b>1</b>₄]­(BF₄)₈), and <b>3</b>·4BF₄^– ([(phen)₄Pd₄<b>L</b>^<b>2</b>₂]­(BF₄)₄) by single-crystal X-ray diffraction analysis. Complexes <b>3</b>–<b>8</b> are square-type hybrid metallomacrocycles, while complexes <b>1</b> and <b>2</b> exhibit folding cyclic structures. Interestingly, in single-crystal structures of <b>1</b>·8BF₄^– and <b>3</b>·4BF₄^–, BF₄^– anions are trapped in the dipalladium clips through anion−π interaction. The luminescence properties and interaction toward anions of these metallomacrocycles were discussed

Addition Reaction-Induced Cluster-to-Cluster Transformation: Controlled Self-Assembly of Luminescent Polynuclear Gold(I) μ₃‑Sulfido Clusters

Unprecedented addition reaction-induced gold­(I) cluster-to-cluster transformation has been observed in the present work. Reaction of the chlorogold­(I) precursor, [vdpp­(AuCl)₂] (vdpp = vinylidenebis­(diphenylphosphine)) containing the diphosphine with unsaturated CC bond, with H₂S resulted in a series of polynuclear gold­(I) μ₃-sulfido clusters bearing Au­(I)···Au­(I) interactions; the identities of which have been fully characterized by NMR, electrospray-ionization mass spectrometry, elemental analysis, and single crystal X-ray diffraction analysis. Diverse research methods, including UV–vis absorption, ¹H NMR, and ³¹P NMR spectroscopy, were employed to detect and monitor the transformation and assembly processes. Supported by single crystal structures, the existence of Au­(I)···Au­(I) bonding interactions sustains the diverse array of sophisticated polynuclear cluster structures and endues them with rich luminescence features

Addition Reaction-Induced Cluster-to-Cluster Transformation: Controlled Self-Assembly of Luminescent Polynuclear Gold(I) μ₃‑Sulfido Clusters

Unprecedented addition reaction-induced gold­(I) cluster-to-cluster transformation has been observed in the present work. Reaction of the chlorogold­(I) precursor, [vdpp­(AuCl)₂] (vdpp = vinylidenebis­(diphenylphosphine)) containing the diphosphine with unsaturated CC bond, with H₂S resulted in a series of polynuclear gold­(I) μ₃-sulfido clusters bearing Au­(I)···Au­(I) interactions; the identities of which have been fully characterized by NMR, electrospray-ionization mass spectrometry, elemental analysis, and single crystal X-ray diffraction analysis. Diverse research methods, including UV–vis absorption, ¹H NMR, and ³¹P NMR spectroscopy, were employed to detect and monitor the transformation and assembly processes. Supported by single crystal structures, the existence of Au­(I)···Au­(I) bonding interactions sustains the diverse array of sophisticated polynuclear cluster structures and endues them with rich luminescence features