Department of Chemistry and Center of Novel Functional Molecules, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, People's Republic of China.
Inorg Chem. 2010 Jan 4;49(1):97-107. doi: 10.1021/ic901521j.
The new ligand dipyrazinyl sulfoxide (also named sulfinyldipyrazine and abbreviated as pyz(2)SO) and a series of its metal complexes including {Ag(pyz(2)SO).CH(3)CN}(infinity) (1), {Ag(pyz(2)SO)}(infinity) (2), Ag(3)(pyz(2)SO)(2)(ClO(4))(3) (3), Ag(pyz(2)SO)(CF(3)CO(2)) (4), {Zn(pyz(2)SO)(H(2)O)(4)(2).H(2)O}(infinity) (5), {Zn(pyz(2)SO)(H(2)O)(2)(2)}(infinity) (6), and {Cd(pyz(2)SO)(2)(H(2)O)(2).H(2)O}(infinity) (7) have been synthesized and characterized by single-crystal X-ray analysis. The counteranions in these complexes prefer to be embraced by a pair of pi-acidic heterocyclic rings via anion-pi interactions, which consequently affect the process of supramolecular assembly. Seven distinct ligation modes of pyz(2)SO involving various bonding combinations of the sulfoxide oxygen and/or pyrazinyl nitrogen atoms (labeled A-G) are observed. Diverse coordination motifs such as (4,4) network, ladder-type, necklace-like, linear, and zigzag-chain structures are found in 1-7. Interestingly, the sulfoxide group of the pyz(2)SO ligand exhibits unusual dipolar sulfinyl...sulfinyl and S=O...pi(pyrazinyl) intermolecular interactions in the supramolecular assemblies of neat pyz(2)SO, 1, and 3-5.
新型配体二吡嗪基亚砜（也称为亚磺酰基二吡嗪，缩写为 pyz(2)SO）及其一系列金属配合物，包括{Ag(pyz(2)SO).CH(3)CN}(infinity) (1)、{Ag(pyz(2)SO)}(infinity) (2)、Ag(3)(pyz(2)SO)(2)(ClO(4))(3) (3)、Ag(pyz(2)SO)(CF(3)CO(2)) (4)、{Zn(pyz(2)SO)(H(2)O)(4)(2).H(2)O}(infinity) (5)、{Zn(pyz(2)SO)(H(2)O)(2)(2)}(infinity) (6)和{Cd(pyz(2)SO)(2)(H(2)O)(2).H(2)O}(infinity) (7)已通过单晶 X 射线分析合成和表征。这些配合物中的抗衡阴离子通过阴离子-π 相互作用更喜欢被一对π-酸性杂环环包裹，这反过来又影响超分子组装过程。观察到 pyz(2)SO 的七种不同的配体模式，涉及亚砜氧和/或吡嗪氮原子的各种键合组合（标记为 A-G）。在 1-7 中发现了各种配位基序，如（4,4）网络、梯形、项链状、线性和锯齿链结构。有趣的是，pyz(2)SO 配体的亚砜基团在纯 pyz(2)SO、1 和 3-5 的超分子组装中表现出不寻常的二极亚磺酰基...亚磺酰基和 S=O...π（吡嗪基）分子间相互作用。
