The synthesis and the luminescence features of three gold(I)‐N‐heterocyclic carbene (NHC) complexes are presented to study how the n‐alkyl group can influence the luminescence properties in the crystalline state. The mononuclear gold(I)‐NHC complexes, [(L1)Au(Cl)] (1), [(L2)Au(Cl)] (2), and [(L3)Au(Cl)] (3) were isolated from the reactions between [(tht)AuCl] and corresponding NHC ligand precursors, [N‐(9‐acridinyl)‐N’‐(n‐butyl)‐imidazolium chloride, (L1.HCl)], [N‐(9‐acridinyl)‐N’‐(n‐pentyl)‐imidazolium chloride, (L2.HCl)] and [N‐(9‐acridinyl)‐N’‐(n‐hexyl)‐imidazolium chloride, (L3.HCl)]. Their single‐crystal X‐ray analysis reveals the influence of the n‐alkyl groups on solid‐state packing. A comparison of the luminescence features of 1–3 with n‐alkyl substituents is explored. The molecules 1–3 depicted blue emission in the solution state, while the yellow emission (for 1), greenish‐yellow emission (for 2), and blue emission (for 3) in the crystalline phase. This paradigm emission shift arises from n‐butyl to n‐pentyl and n‐hexyl in the crystalline state due to the carbon‐carbon rotation of the n‐alkyl group, which tends to promote unusual solid packing. Hence n‐alkyl group adds a novel emission property in the crystalline state. Density Functional Theory and Time‐Dependent Density Functional Theory calculations were carried out for monomeric complex, N‐(9‐acridinyl)‐N’‐(n‐heptyl)imidazole‐2‐ylidene gold(I) chloride and dimeric complex, N‐(9‐acridinyl)‐N’‐(n‐heptyl)imidazole‐2‐ylidene gold(I) chloride to understand the structural and electronic properties.
Novel antimony(III) imidazole selone complexes under a super crowded environment are reported for the first time. The super bulky selone antimony complexes, [{IPr*Se}(SbCl3)2] (1) and [IPr*Se(SbBr3)2] (2), were isolated from...
The novel LnIII {Ln = Dy (1 ‑Dy ), Gd (2 ‑Gd ), and La (3 ‑La )} benzimidazolium tricarboxylate coordination polymers have been synthesized, and their magnetic properties have been investigated. Single-crystal X-ray analysis revealed that 1 ‑Dy , 2 ‑Gd , and 3 ‑La are one-dimensional coordination polymers with general molecular formulas of {[Ln(L)2(H2O)4]·(6Br)}∞ [L = 3,3′,3′′-((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene))tris(1-(carboxymethyl)-benzimidazolium)], which crystallized in the monoclinic, P21 /c space group. The solid-state packing of these coordination polymers shows the spiral propagation in a one-dimensional direction. The direct current (dc) magnetic data (susceptibility and magnetization) were collected for 1 ‑Dy and 2 ‑Gd . The alternating current (ac) magnetic measurement for 1 ‑Dy at zero field shows the characteristic signature of single-molecule magnets (SMMs) at low temperatures but without clear maxima. Further, to rationalize the experimentally observed magnetic behavior and to understand the factors affecting the dynamic magnetic behavior of 1 ‑Dy , we performed detailed completed active space self-consistent field (CASSCF) based calculations on 1 ‑Dy . Our detailed theoretical analysis suggests that the hydrogen bonding interaction between the coordinated water molecule and the Br– counteranion increases the equatorial electron density, eradicating the slow relaxation in 1 ‑Dy .
The catalytic application of bismuth(III) coordination polymer has been reported. Dinuclear bismuth(III) chalcogenone complexes [(L1)2BiCl2(μ2-Cl)]2 (1), [(L2)2BiBr2(μ2-Br)]2 (4), 2D layered bismuth(III) thione complex [{(L2)BiCl2(μ2-Cl)}2]∞ (2), and 1D chain [(L1)Bi(Br)(μ2-Br)2.CH3CN]∞ (3)...
Sustainable noble metal-N-heterocyclic carbenes (NHC's) are a topic of arising concern in both the chemical industry and the academic community due to a growing consciousness of environmental pollution and scarcity. Recovering and reusing homogeneous catalysts from the reaction mixture requires a tremendous amount of capital investment in the chemical manufacturing industry. Heterogeneous catalysts are proved to have better functional groups tolerance; however, catalysts support largely influences the active catalyst sites to affect catalyst efficiency and selectivity. Thus the, choice of catalyst supports plays an almost decisive role in this emerging area of catalysis research. Graphene oxide (GO)/reduced graphene oxide (rGO) support has a potential growth in heterogeneous catalysis owing to their commercial availability, considerably larger surface area, inert towards chemical transformations, and easy surface functionalization to attached metal complexes via covalent and non-covalent aromatic π-conjugates.To take advantage of two independently well-established research areas of noble metal-N-heterocyclic carbenes and GO/rGO support via covalent or non-covalent interactions approach would offer novel heterogeneous complexes with improved catalytic efficiency without sacrificing product selectivity. This unique concept of marrying metal-N-heterocyclic carbenes with GO/rGO support has potential growth in the chemical and pharmaceutical industry, however, limited examples are reported in the literature. In this perspective, a comprehensive summary of metalÀ NHC synthesis on GO/rGO support and synthetic strategies to graft MÀ NHC onto GO/ rGO surface, catalytic efficiency, for the catalytic transformation are critically reviewed. Furthermore, a plausible mechanism for non-covalent grafting methodology is summarized to direct readers to give a better understanding of MÀ NHC@rGO complexes. This would also allow the designing of engineered catalysts for unexplored catalytic applications.
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