Intriguing diaza effects on magnetic coupling characteristics in diaza‐benzo[        <i >kk        ]tetraphene‐bridged nitroxide diradicals

Zhang Fengying; Luo Qi; Song Xiufang; Song Xinyu; Bu Yuxiang

摘要

Abstract > We theoretically design four diaza‐benzo[ k ]tetraphene‐based diradical isomers ( 1, 2, 3 , and 4 ) with two nitroxide (NO) radical groups as spin sources. The calculations at the B3LYP/6‐311++G(d,p) level suggest that the diaza doping can induce the aromaticity changes and the C?C bond rearrangements and, thus, remarkably affect their magnetic coupling magnitudes and even characteristics (ferromagnetic vs. antiferromagnetic). More interestingly, different diaza‐doping positions can lead to distinctly different effects, and further dielectron‐oxidation can also noticeably change the magnetic coupling magnitudes from ?919.9?cm ?1 ( 1 ) to ?158.3?cm ?1 ( 1 2+ ) or from ?105.1?cm ?1 ( 3 ) to ?918.9?cm ?1 ( 3 2+ ) or induce the magnetic conversions from nonmagnetism ( 2 ) to antiferromagnetism ( 2 2+ , ?140.1?cm ?1 ) or from ferromagnetism ( 4 , 108.9?cm ?1 ) to antiferromagnetism ( 4 2+ , ?462.5?cm ?1 ). Good matching of two singly occupied molecular orbitals (SOMOs) of the NO groups with the highest occupied molecular orbital (HOMO) of the coupler (for 1 ), or with the lowest unoccupied molecular orbital (LUMO) of the coupler (for 3 2 </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”> <title type =“main”>抽象</ title> >我们理论上设计四个diaza-benzo [ k </ i>] taphene-基于具有两种氮氧化物（NO）基团作为旋转源的基于Diradical异构体（ 1,2,3 / b>，和 4℃）。 B3Lyp / 6-311 ++ g（d，p）水平的计算表明，Diaza掺杂可以诱导芳香性变化和C键重排，因此显着影响它们的磁耦合幅度甚至特征（铁磁vs.反铁磁）。更有趣的是，不同的Diaza掺杂位置可以导致明显不同的效果，并且进一步的介质氧化也可以显着改变来自α1919.9Ω·cm （ 1 </ b的磁耦合幅度>）至？158.3？cm ？1 </ sup>（ 1 </ b> 2 + </ b> </ sup>）或from？105.1？cm <sup >？1 </ sup>（ 3 </ b>）至α918.9？cm Δ1</ sup>（ 3 </ b> 2 + </ b> </ sup>）或诱导来自非磁性（ 2）的磁性转换（ 2 </ b>）反铁磁性（ 2 </ b> 2 + </ b> </ sup >，？140.1？cm α1</ sup>）或从铁磁性（ 4 </ b>，108.9？cm 1 </ sup>）到反铁磁体（ 4 / b> 2 + </ b> </ sup>，？462.5？cm ？1 </ sup>）。与偶联剂最高占用的分子轨道（HOMO）的两个单独占用的分子轨道（SOMOS）的良好匹配（对于 1 </ b>），或与最低的未占用的分子轨道（LUMO）耦合器（对于 3 </ b> 2 </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>2018年第18期</span><b style="margin: 0 2px;">|</b><span>共17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=Zhang Fengying&option=202" target="_blank" rel="nofollow">Zhang Fengying;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Luo Qi&option=202" target="_blank" rel="nofollow">Luo Qi;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Song Xiufang&option=202" target="_blank" rel="nofollow">Song Xiufang;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Song Xinyu&option=202" target="_blank" rel="nofollow">Song Xinyu;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Bu Yuxiang&option=202" target="_blank" rel="nofollow">Bu Yuxiang;</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>School of Chemistry and Chemical EngineeringShandong UniversityJinan 250100 People's Republic of China;</p> <p>School of Chemistry and Chemical EngineeringShandong UniversityJinan 250100 People's Republic of China;</p> <p>School of Chemistry and Chemical EngineeringShandong UniversityJinan 250100 People's Republic of China;</p> <p>School of Chemistry and Chemical EngineeringShandong UniversityJinan 250100 People's Republic of China;</p> <p>School of Chemistry and Chemical EngineeringShandong UniversityJinan 250100 People's Republic of China;</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=benzoktetraphene‐based magnet design&option=203" rel="nofollow">benzoktetraphene‐based magnet design;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=counterion effect&option=203" rel="nofollow">counterion effect;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=density functional theory calculations&option=203" rel="nofollow">density functional theory calculations;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=diaza‐positional effect&option=203" rel="nofollow">diaza‐positional effect;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=redox regulation&option=203" rel="nofollow">redox regulation;</a> </p> <div class="translation"> 机译：苯并[K]四丙基磁铁设计;抗衡效应;密度函数理论计算;Diaza - 位置效应;氧化还原调节; 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href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=汤振兵&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">,汤振兵</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=马良财&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">,马良财</a> <span> <a href="/journal-cn-4713/" target="_blank" rel="nofollow" class="tuijian_authcolor"> . 陕西师范大学学报（自然科学版） </a> </span> <span> . 2019</span><span>,第002期</span> </span> </div> </li> <li> <div> <b>6. </b><a class="enjiyixqcontent" href="/academic-conference-cn_meeting-22898_thesis/02022740075.html">几种不同偶联剂对纳米磁性粒子的影响</a> <b>[C]</b> <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=赵慧君&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor"> . 赵慧君</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=张中杰&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">,张中杰</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=张国鹏&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">,张国鹏</a> <span> <a href="/conference-cn-22898/" target="_blank" rel="nofollow" class="tuijian_authcolor"> . 2006年全国功能材料学术年会 </a> <span> <span> . 2006</span> </span> </div> </li> <li> <div> <b>7. </b><a class="enjiyixqcontent" href="/academic-degree-domestic_mphd_thesis/020314262005.html">低温高场下顺磁性物质的磁和磁光特性及掺杂影响MnZn功率铁氧体磁性能的研究</a> <b>[A] </b> <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=顾明&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor"> . 顾明</a> <span> . 2008</span> </span> </div> </li> </ul> <ul style="display: none;"> <li> <div> <b>1. </b><a class="enjiyixqcontent" href="/patent-detail/061202860675.html">包括桥接单元的用于影响和/或检测磁性粒子的装置和方法</a> <b>[P]</b> . <span> 中国专利： CN105078451B </span> <span> . 2018.05.15</span> </div> </li> <li> <div> <b>2. </b><a class="enjiyixqcontent" href="/patent-detail/06120107573226.html">包括桥接单元的用于影响和/或检测磁性粒子的装置和方法</a> <b>[P]</b> . <span> 中国专利： CN105078451A </span> <span> . 2015-11-25</span> </div> </li> <li> <div> <b>3. </b><a class="enjiyixqcontent" href="/patent-detail/06130406757413.html">Diaza-benzo fluoranthene compound</a> <b>[P]</b> . <span> 外国专利：  BR112017016819A2 </span> <span> . 2018-04-03</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：二氮杂苯并荧蒽化合物 </span> </p> </li> <li> <div> <b>4. </b><a class="enjiyixqcontent" href="/patent-detail/06130420332287.html">4-(5-benzo1,3-dioxol-5-yl-1,3,4 oxadiazol-2-yl)-1,4-diaza-bicyclo3.2.2nonane and pharmaceutical compositions comprising it</a> <b>[P]</b> . <span> 外国专利：  IL193925A </span> <span> . 2013-08-29</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：4-（5-苯并[1,3]-二恶唑-5-基-[1,3,4]恶二唑-2-基）-1,4-二氮杂双环[3.2.2]壬烷及其药物组合物 </span> </p> </li> <li> <div> <b>5. </b><a class="enjiyixqcontent" href="/patent-detail/06130430357205.html">4-(5-BENZO1,3-DIOXOL-5-YL-1,3,4 OXADIAZOL-2-YL)-1,4-DIAZA-BICYCLO3.2.2NONANE AND A PHARMACEUTICAL COMPOSITION COMPRISING THEREOF</a> <b>[P]</b> . <span> 外国专利：  IL193925A </span> <span> . 2009-06-15</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：4-（5-苯并[1,3]-二恶唑-5-基-[1,3,4]恶二唑-2-基）-1,4-二氮杂双环[3.2.2]壬烷和一种药物组成因此 </span> </p> </li> </ul> </div> </div> </div> <div class="theme cardcommon" style="overflow: auto;display:none"> <h3 class="all_title" id="enpatent55">相关主题</h3> <ul id="subject"> </ul> </div> </div> </div> </div> <div class="right rightcon"> <div class="details_img cardcommon clearfix" style="margin-bottom: 10px;display:none;" > </div> </div> 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Intriguing diaza effects on magnetic coupling characteristics in diaza‐benzo[ kk ]tetraphene‐bridged nitroxide diradicals

摘要