Kumar Sandeep, Chaudhri Nivedita, Osterloh W Ryan, Kadish Karl M, Sankar Muniappan
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247667, India.
Department of Chemistry, University of Houston, Houston, TX, 77204-5003, USA.
Dalton Trans. 2021 Nov 30;50(46):17086-17100. doi: 10.1039/d1dt03122h.
A series of nickel(II) monobenzochlorins (MBCs) and monobenzoporphyrins (MBPs) containing -appended or ,-fused indanedione (IND) or malononitrile (MN) groups were synthesized and characterized for their physicochemical, electrochemical and anion sensing properties. Each investigated compound contained four -phenyl rings and a single ,'-fused 4,5-di(methoxycarbonyl)benzene ring, with the chlorins represented as NiMBC(Y)(R) and the porphyrins as NiMBP(Y), where Y is an indanedione (IND) or malononitrile (MN) group, R = H or Br and Y is a ,-fused IND or MN substituent. One of the investigated compounds, NiMBP(IND), was structurally characterized and shown to possess a macrocyclic conformation. The monobenzochlorins, NiMBC(IND), NiMBC(IND)Br and NiMBC(MN), reversibly respond to basic anions such as CN, F, OAc and HPO through a visible color change assigned to the deprotonation of the vicinal proton on the appended IND or MN substituents. The malononitrile-fused Ni monobenzoporphyrin, NiMBP(MN), exhibited a selective but irreversible visual detection of cyanide ions (LOD = 2.23 ppm). This reaction afforded a tri-fused π-extended monobenzoporphyrin product represented as NiMBP(VCN) (where VCN = ,-fused vinyl cyanide) in non-aqueous media and proceeded anion induced electron transfer (AIET). The generated π-extended porphyrin was also isolated and characterized as to its physicochemical and electrochemical properties and found to possess a narrow electrochemical HOMO-LUMO gap of 1.46 V along with a near-IR (NIR) absorption band located at 861 nm.
合成了一系列含有 - 附加或 ,- 稠合茚二酮（IND）或丙二腈（MN）基团的镍（II）单苯并二氢卟啉（MBCs）和单苯并卟啉（MBPs），并对其物理化学、电化学和阴离子传感特性进行了表征。每个研究的化合物都含有四个 - 苯基环和一个单一的 ,'- 稠合 4,5 - 二（甲氧基羰基）苯环，二氢卟啉表示为 NiMBC(Y)(R)，卟啉表示为 NiMBP(Y)，其中 Y 是茚二酮（IND）或丙二腈（MN）基团，R = H 或 Br，Y 是一个 ,- 稠合的 IND 或 MN 取代基。所研究的化合物之一 NiMBP(IND) 进行了结构表征，显示具有 大环构象。单苯并二氢卟啉 NiMBC(IND)、NiMBC(IND)Br 和 NiMBC(MN) 通过与附加的 IND 或 MN 取代基上邻位质子去质子化相关的可见颜色变化，对诸如 CN、F、OAc 和 HPO 等碱性阴离子产生可逆响应。丙二腈稠合的镍单苯并卟啉 NiMBP(MN) 对氰离子表现出选择性但不可逆的视觉检测（检测限 = 2.23 ppm）。该反应在非水介质中生成了一种表示为 NiMBP(VCN)（其中 VCN = ,- 稠合乙烯基氰）的三稠合 π 扩展单苯并卟啉产物，并进行了阴离子诱导电子转移（AIET）。生成的 π 扩展卟啉也被分离出来，并对其物理化学和电化学性质进行了表征，发现其具有 1.46 V 的窄电化学 HOMO - LUMO 能隙以及位于 861 nm 的近红外（NIR）吸收带。
