A theoretical insight into the role of counter anions and their interactions in nitropentaamminecobalt(III) toward linkage isomerism‐induced photochemical motion

Muya Jules Tshishimbi; Meher Biswa Ranjan; Sahoo Subash Chandra; Chung Hoeil

摘要

Abstract > Density functional theory (B3LYP, B3LYP‐D3, wB97XD, M062X, and M06L) and ab initio methods (MP2 and CCSD(T)) in conjunction with 6‐31+G(d,p) and LanL2DZ were employed to investigate the interaction energies between [Co(NH <sub>3</sub> ) <sub>5</sub> NO <sub>2</sub> ] 2+ linkage isomers and chloride and nitrate in both gas phase and solid state. The nature of the chemical bonding has been analyzed by means of the atoms in molecules, electron density shift, natural bond orbitals, symmetry adapted perturbation theory, and energy decomposition analysis. The electronic structures of the two lowest laying singlet states (S <sub>o</sub> and S <sub>1</sub> ) of [Co(NH <sub>3</sub> ) <sub>5</sub> NO <sub>2</sub> ](NO <sub>3</sub> )Cl isomers were also investigated using CASSCF(6,6) with LanL2DZ and 6‐31G(d) basis sets. Our results show that [Co(NH <sub>3</sub> ) <sub>5</sub> NO <sub>2</sub> ] 2+ linkage isomers interact more strongly with chloride than nitrate. The structures of [Co(NH <sub>3</sub> ) <sub>5</sub> NO <sub>2</sub> ](NO <sub>3</sub> )Cl linkage isomers and their relative stabilities were examined in gas phase and in solid state and confirmed the nitro‐complex as the most stable following by a viable intermediate endo ‐complex. Study of the nitro‐nitrito linkage isomerization in [Co(NH <sub>3</sub> ) <sub>5</sub> NO <sub>2</sub> ](NO <sub>3</sub> )Cl revealed that anions form strong electrostatic bonds with [Co(NH </span> <span class="z_kbtn z_kbtnclass hoverxs" style="display: none;">展开▼</span> </div> <div class="translation abstracttxt"> <span class="zhankaihshouqi fivelineshidden" id="abstract"> <span>机译：</span><Abstract Type =“Main”XML：Lang =“en”> <标题类型=“main”>抽象</ title> >密度泛函理论（B3LYP，B3LYP-D3，WB97XD，M062x和M06L）和AB与6-31 + G（D，P）和LANL2DZ一起使用的Initio方法（MP2和CCSD（T））研究[CO（NH <SUB> 3 </ sub>）<sub> 5之间的相互作用能量</ sub> No <sub> 2 </ sub>] 2 + </ sup>链接异构体和氯化物，硝酸盐在气相和固态中。通过分子中的原子，电子密度移位，天然键轨道，对称性适应的扰动理论和能量分解分析，已经通过原子分析了化学键的性质。 [CO（NH <SUB> 3 </ sub>）<sub> 5 <sab> 5 <sim> 5 <sub> s <sub> 1 </ sub>）的两个最低敷定单态的电子结构/ sub> NO <sub> 2 </ sub>]（NO <sub> 3 </ sub>）Cl异构体也使用CASSCF（6,6）进行LANL2DZ和6-31G（D）基集。我们的结果表明，[CO（NH <sub> 3 </ sub>）<sub> 5 </ sub> no <sub> 2 </ sub>] 2 + </ sup>连接异构体与之相互作用氯化物比硝酸盐。 [CO（NH <sub> 3 </ sub>）<sub> 5 </ sub> no <sub> 2 </ sub>]（no <sub> 3 </ sub>）cl链接异构体及其在气相和固态中检查相对稳定性，并通过可行中间体ench-in-complec用剂证实了硝基复合物作为最稳定的后络合物。 [CO（NH <SUB> 3 </ SUB> NO <SUB> 2 </ sub> [SUA> 5 </ sub> NO <sub> 2 </ sub>]硝基 - 硝基键化异构化的研究（NO <SUB> 3 </ sub> ）CL显示阴离子与[CO（NH）形成强静电键 </span> <span class="z_kbtn z_kbtnclass hoverxs" style="display: none;">展开▼</span> </div> </div> <div class="record"> <h2 class="all_title" id="enpatent33" >著录项</h2> <ul> <li> <span class="lefttit">来源</span> <div style="width: 86%;vertical-align: text-top;display: inline-block;"> <a href='/journal-foreign-21753/'>《International Journal of Quantum Chemistry》</a> <b style="margin: 0 2px;">|</b><span>2019年第14期</span><b style="margin: 0 2px;">|</b><span>共16页</span> </div> </li> <li> <div class="author"> <span class="lefttit">作者</span> <p id="fAuthorthree" class="threelineshidden zhankaihshouqi"> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Muya Jules Tshishimbi&option=202" target="_blank" rel="nofollow">Muya Jules Tshishimbi;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Meher Biswa Ranjan&option=202" target="_blank" rel="nofollow">Meher Biswa Ranjan;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Sahoo Subash Chandra&option=202" target="_blank" rel="nofollow">Sahoo Subash Chandra;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Chung Hoeil&option=202" target="_blank" rel="nofollow">Chung Hoeil;</a> </p> <span class="z_kbtnclass z_kbtnclassall hoverxs" id="zkzz" style="display: none;">展开▼</span> </div> </li> <li> <div style="display: flex;"> <span class="lefttit">作者单位</span> <div style="position: relative;margin-left: 3px;max-width: 639px;"> <div class="threelineshidden zhankaihshouqi" id="fOrgthree"> <p>Department of ChemistryHanyang UniversitySeoul South Korea;</p> <p>Department of BotanyComputational Biology and Bioinformatics Laboratory Berhampur UniversityBerhampur Odisha India;</p> <p>Department of ChemistryPanjab UniversityChandigarh India;</p> <p>Department of ChemistryHanyang UniversitySeoul South Korea;</p> </div> <span class="z_kbtnclass z_kbtnclassall hoverxs" id="zhdw" style="display: none;">展开▼</span> </div> </div> </li> <li > <span class="lefttit">收录信息</span> <span style="width: 86%;vertical-align: text-top;display: inline-block;"></span> </li> <li> <span class="lefttit">原文格式</span> <span>PDF</span> </li> <li> <span class="lefttit">正文语种</span> <span>eng</span> </li> <li> <span class="lefttit">中图分类</span> <span><a href="https://www.zhangqiaokeyan.com/clc/1186.html" title="物理化学（理论化学）、化学物理学">物理化学（理论化学）、化学物理学;</a></span> </li> <li class="antistop"> <span class="lefttit">关键词</span> <p style="width: 86%;vertical-align: text-top;"> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=interaction energies&option=203" rel="nofollow">interaction energies;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=linkage isomers&option=203" rel="nofollow">linkage isomers;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=nitropentaamminecobalt(III)&option=203" rel="nofollow">nitropentaamminecobalt(III);</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=photosalient effect&option=203" rel="nofollow">photosalient effect;</a> </p> <div class="translation"> 机译：互动能量;联动异构体;硝基丁酰胺钴（III）;光良效果; 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