Dipyridylamine-Functionalized N-Heterocyclic Carbene Ligands for Structurally Diverse Silver(I) and Gold(I) Complexes: Topology, Metallophilic Interactions, and Structure–Property Relationships

IF 4.6 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-06 DOI:10.1021/acs.inorgchem.6c03372

Xun-Rong Wang, Zhi-Lin Wang, Su-Ying Chien, Shao-An Hua

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Abstract

Macrocyclic N-heterocyclic carbene (NHC) ligands incorporating multidentate donor motifs offer opportunities for constructing structurally diverse coordination complexes. Herein we report a family of dipyridylamine (DPA)-functionalized NHC ligands comprising acyclic ([H₂L¹](PF₆)₂) and macrocyclic architectures ([H₄L²](OTf)₄ and [H₄L³](OTf)₄) with distinct coordination topologies. Structural studies reveal linker-dependent ligand conformations ranging from Z-shaped and double-V structures to folded and extended macrocycles, enabling tunable cavity sizes and coordination environments. Metalation with Ag(I) and Au(I) affords mono-, di-, and trinuclear complexes. The trinuclear silver complex [(AgL¹)₂Ag](PF₆)₃ and heterometallic complex [(AuL¹)₂Ag](PF₆) feature short metal–metal separations consistent with metallophilic interactions. In solution, DOSY NMR and mass spectrometry identify [AgL¹]⁺ and [AuL¹]⁺ as the predominant species, suggesting dissociation of the trinuclear assemblies. Variable-temperature NMR and thermodynamic analyses reveal comparable exchange dynamics for the ethylene-linked [Ag₂L²](OTf)₂ and [Au₂L²](OTf)₂. Selected complexes exhibit enhanced solid-state luminescence arising from cooperative π–π stacking and metallophilic interactions, whereas antibacterial studies reveal enhanced activity upon metal coordination, with the Ag(I) complexes showing pronounced activity toward Escherichia coli (E. coli) and the Au(I) complexes exhibiting greater solution stability and broader antibacterial activity. These results establish DPA-functionalized NHC ligands as versatile platforms for coinage-metal assemblies with tunable topology, metal–metal interactions, photophysical properties, and biological activity.

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结构多样银(I)和金(I)配合物的二吡啶胺功能化n -杂环卡宾配体：拓扑结构、亲金相互作用和结构-性能关系

含有多齿给体基序的大环n -杂环碳（NHC）配体为构建结构多样的配合物提供了机会。本文报道了一类具有不同配位拓扑结构的双吡啶胺（DPA）功能化NHC配体，包括无环结构（[H2L1](PF6)2）和大环结构([H4L2]（OTf)4和[H4L3](OTf)4）。结构研究揭示了连接体依赖的配体构象，从z形和双v结构到折叠和扩展的大环，实现了可调的腔大小和配位环境。银(I)和金(I)的金属化可以得到单核、二核和三核配合物。三核银配合物[(AgL1)2Ag](PF6)3和异金属配合物[(AuL1)2Ag]（PF6）具有与亲金属相互作用一致的短金属-金属分离特征。在溶液中，DOSY NMR和质谱鉴定[AgL1]+和[AuL1]+为优势种，表明三核组合的解离。变温核磁共振和热力学分析表明，乙烯链[Ag2L2](OTf)2和[Au2L2](OTf)2的交换动力学相似。选定的配合物表现出由于π -π的协同堆积和亲金属相互作用而增强的固态发光，而抗菌研究显示金属配位的活性增强，其中Ag(I)配合物对大肠杆菌（E. coli）表现出明显的活性，Au(I)配合物表现出更大的溶液稳定性和更广泛的抗菌活性。这些结果建立了dpa功能化NHC配体作为具有可调拓扑结构、金属-金属相互作用、光物理性质和生物活性的合成金属组装的通用平台。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.