{"title":"用于 DSSC 的 N-杂环羰基和多吡啶配体钌 (II) 光敏剂中的锚基效应:计算评估","authors":"Angelina Mary and Abbas Raja Naziruddin","doi":"10.1039/D4NJ03729D","DOIUrl":null,"url":null,"abstract":"<p >In this work, we evaluate the bonding characteristics and interfacial electron transfer dynamics of three heteroleptic ruthenium photosensitizers featuring different terpyridine (tpy) acceptor end configurations through quantum-chemical calculations. These photosensitizers feature tpy ligands with a mono/tricarboxylic acid or a phenyl-carboxylic acid anchor and a <em>trans</em>-disposed –NCS and <em>N</em>-heterocyclic carbene ligand in a C^N donor set. Adiabatic transitions reveal significant overlap between higher-excited and ground-state orbitals and correlate with the experimentally observed anti-Kasha fluorescence. In all complexes, two carboxylate-<em>O</em> atoms of the central anchor effectively bind with TiO<small><sub>2</sub></small> by bridging two titanium sites. However, appending an additional anchor on each peripheral pyridine of tpy renders binding through only one anchor's –C<img><em>O</em> atom to TiO<small><sub>2</sub></small>. Contrary to the complex bearing three anchors, those featuring monocarboxylate-functionalized tpy exhibit faster electron injection within 100 fs. In all, this study provides insights into the photosensitization attributes of the ruthenium complexes for dye-sensitized solar cells.</p>","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Anchor group effects in ruthenium(ii) photosensitizers bearing N-heterocyclic carbene and polypyridyl ligands for DSSCs: a computational evaluation†\",\"authors\":\"Angelina Mary and Abbas Raja Naziruddin\",\"doi\":\"10.1039/D4NJ03729D\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >In this work, we evaluate the bonding characteristics and interfacial electron transfer dynamics of three heteroleptic ruthenium photosensitizers featuring different terpyridine (tpy) acceptor end configurations through quantum-chemical calculations. These photosensitizers feature tpy ligands with a mono/tricarboxylic acid or a phenyl-carboxylic acid anchor and a <em>trans</em>-disposed –NCS and <em>N</em>-heterocyclic carbene ligand in a C^N donor set. Adiabatic transitions reveal significant overlap between higher-excited and ground-state orbitals and correlate with the experimentally observed anti-Kasha fluorescence. In all complexes, two carboxylate-<em>O</em> atoms of the central anchor effectively bind with TiO<small><sub>2</sub></small> by bridging two titanium sites. However, appending an additional anchor on each peripheral pyridine of tpy renders binding through only one anchor's –C<img><em>O</em> atom to TiO<small><sub>2</sub></small>. Contrary to the complex bearing three anchors, those featuring monocarboxylate-functionalized tpy exhibit faster electron injection within 100 fs. In all, this study provides insights into the photosensitization attributes of the ruthenium complexes for dye-sensitized solar cells.</p>\",\"PeriodicalId\":95,\"journal\":{\"name\":\"New Journal of Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-09-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"New Journal of Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/nj/d4nj03729d\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"New Journal of Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/nj/d4nj03729d","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Anchor group effects in ruthenium(ii) photosensitizers bearing N-heterocyclic carbene and polypyridyl ligands for DSSCs: a computational evaluation†
In this work, we evaluate the bonding characteristics and interfacial electron transfer dynamics of three heteroleptic ruthenium photosensitizers featuring different terpyridine (tpy) acceptor end configurations through quantum-chemical calculations. These photosensitizers feature tpy ligands with a mono/tricarboxylic acid or a phenyl-carboxylic acid anchor and a trans-disposed –NCS and N-heterocyclic carbene ligand in a C^N donor set. Adiabatic transitions reveal significant overlap between higher-excited and ground-state orbitals and correlate with the experimentally observed anti-Kasha fluorescence. In all complexes, two carboxylate-O atoms of the central anchor effectively bind with TiO2 by bridging two titanium sites. However, appending an additional anchor on each peripheral pyridine of tpy renders binding through only one anchor's –CO atom to TiO2. Contrary to the complex bearing three anchors, those featuring monocarboxylate-functionalized tpy exhibit faster electron injection within 100 fs. In all, this study provides insights into the photosensitization attributes of the ruthenium complexes for dye-sensitized solar cells.