{"@context":{"@vocab":"https://cir.nii.ac.jp/schema/1.0/","rdfs":"http://www.w3.org/2000/01/rdf-schema#","dc":"http://purl.org/dc/elements/1.1/","dcterms":"http://purl.org/dc/terms/","foaf":"http://xmlns.com/foaf/0.1/","prism":"http://prismstandard.org/namespaces/basic/2.0/","cinii":"http://ci.nii.ac.jp/ns/1.0/","datacite":"https://schema.datacite.org/meta/kernel-4/","ndl":"http://ndl.go.jp/dcndl/terms/","jpcoar":"https://github.com/JPCOAR/schema/blob/master/2.0/"},"@id":"https://cir.nii.ac.jp/crid/1390282680256199040.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.3175/molsci.2.a0019"}},{"identifier":{"@type":"NAID","@value":"130002126187"}}],"dc:title":[{"@language":"en","@value":"Direct Observation of the Intramolecular Structural Change and the Solvent Reorientation Process in the Intramolecular Charge-Transfer Reaction"},{"@language":"ja","@value":"過渡赤外分光法を用いた分子内電荷移動反応における分子内構造変形と溶媒再配向過程の直接観測"}],"dc:language":"ja","description":[{"type":"abstract","notation":[{"@language":"en","@value":"The intramolecular charge-transfer (ICT) reaction is characterized by intra- and inter-molecular structural changes. A well-known example of the former is a twist around the single bond between the charge accepting and donating groups of the reactant itself. The latter is a reorientation of solvent molecules against the reactant to stabilize the energy of the system. Detailed information about such structural change should provide us with an insight for a well understanding of the ICT reaction. Thus, we have carried out transient infrared (IR) absorption spectroscopy of jet-cooled (<i>p</i>-cyanophenyl) pentamethyldisilane (CPDS) and its solvated clusters. We have succeeded in observing transient IR spectra of the CT state, exhibiting very distinct patterns compared with those of the electronic ground state. Combined with results of quantum chemical calculations, we determined the equilibrium structure of the CT state of CPDS monomer. Our result is clear evidence that the twist occurs in the ICT process, as expected. In addition, we found a step-wise process in the case of solvated clusters based on our transient IR spectra. This process was related to the solvent reorientation in the ICT reaction. The observed spectra enabled us to determine very precise information about the reorientation process such as the initial and final orientations of the solvent molecule(s). These findings should provide us with a deep insight for understanding the ICT reaction."}],"abstractLicenseFlag":"disallow"}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1410290697239480064","@type":"Researcher","personIdentifier":[{"@type":"NRID","@value":"9000017708997"}],"foaf:name":[{"@language":"en","@value":"Ishikawa Haruki"},{"@language":"ja","@value":"石川 春樹"}],"jpcoar:affiliationName":[{"@language":"en","@value":"Department of Chemistry, Graduate School of Science, Kobe University"},{"@language":"ja","@value":"神戸大学大学院 理学研究科 化学専攻"}]}],"publication":{"publicationIdentifier":[{"@type":"EISSN","@value":"18818404"}],"prism:publicationName":[{"@language":"en","@value":"Molecular Science"},{"@language":"en","@value":"Mol. Sci."}],"dc:publisher":[{"@language":"en","@value":"Japan Society for Molecular Science"},{"@language":"ja","@value":"分子科学会"}],"prism:publicationDate":"2008","prism:volume":"2","prism:number":"1","prism:startingPage":"A0019"},"reviewed":"false","availableAt":"2008","foaf:topic":[{"@id":"https://cir.nii.ac.jp/all?q=solvated%20clusters","dc:title":"solvated clusters"},{"@id":"https://cir.nii.ac.jp/all?q=transient%20IR%20spectroscopy","dc:title":"transient IR spectroscopy"},{"@id":"https://cir.nii.ac.jp/all?q=intramolecular%20charge-transfer%20reaction","dc:title":"intramolecular charge-transfer reaction"},{"@id":"https://cir.nii.ac.jp/all?q=phenyldisilane","dc:title":"phenyldisilane"},{"@id":"https://cir.nii.ac.jp/all?q=solvent%20reorientation","dc:title":"solvent reorientation"}],"relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1050001202761495168","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Structures and the vibrational relaxations of size-selected benzonitrile-(H2O)n=1-3 and -(CH3OH)n=1-3 clusters studied by fluorescence detected Raman and infrared spectroscopies"}]},{"@id":"https://cir.nii.ac.jp/crid/1360292618703493120","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Chemistry of organosilicon compounds. 300. .sigma..pi.* Orthogonal intramolecular charge-transfer (OICT) excited states and photoreaction mechanism of trifluoromethyl-substituted phenyldisilanes"}]},{"@id":"https://cir.nii.ac.jp/crid/1360855570227561088","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Promotion of intramolecular charge transfer in dimethylamino derivatives: twisting versus acceptor-group rehybridization"}]},{"@id":"https://cir.nii.ac.jp/crid/1360855570384483200","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Direct observation of the solvent reorientation dynamics in the “twisted” intramolecular charge-transfer process of cyanophenyldisilane–water cluster by transient infrared spectroscopy"}]},{"@id":"https://cir.nii.ac.jp/crid/1360855571020725760","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Reinterpretation of the anomalous fluorescense of  -n,n-dimethylamino-benzonitrile"}]},{"@id":"https://cir.nii.ac.jp/crid/1360855571135156096","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Classification of Spectra of Cata-Condensed Hydrocarbons"}]},{"@id":"https://cir.nii.ac.jp/crid/1360865815496817536","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Enhancement of the blue luminescence of phenylquinoline derivatives by cation addition"}]},{"@id":"https://cir.nii.ac.jp/crid/1361137045942237312","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Spectroscopic Investigation on the Microscopic Solvation Effect on the Intramolecular Charge-Transfer Process of (<i>p</i>-Cyanophenyl)pentamethyldisilane in Supersonic Jets"}]},{"@id":"https://cir.nii.ac.jp/crid/1361418519278052864","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Vibrational Spectroscopy of Small Br<sup>-</sup>·(H<sub>2</sub>O)<i><sub>n</sub></i> and I<sup>-</sup>·(H<sub>2</sub>O)<i><sub>n</sub></i> Clusters:  Infrared Characterization of the Ionic Hydrogen Bond"}]},{"@id":"https://cir.nii.ac.jp/crid/1361418520216267904","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Intramolecular 2pπ* → 3dπ charge transfer in the excited state of phenyldisilane studied by picosecond and nanosecond laser spectroscopy"}]},{"@id":"https://cir.nii.ac.jp/crid/1361699995195853056","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Evidence that the fluorescence of phenyldisilanes involves the<sup>1</sup>(2pπ, 3dπ) intramolecular charge-transfer state"}]},{"@id":"https://cir.nii.ac.jp/crid/1361699995530333696","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Photochemical and photophysical behaviour of phenylsilanes and naphthylsilanes"}]},{"@id":"https://cir.nii.ac.jp/crid/1361981471023961344","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Assignments of near-ultraviolet absorption and intramolecular charge-transfer emission in phenylpentamethyldisilane"}]},{"@id":"https://cir.nii.ac.jp/crid/1362262945322636800","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Structural Changes Accompanying Intramolecular Electron Transfer:  Focus on Twisted Intramolecular Charge-Transfer States and Structures"}]},{"@id":"https://cir.nii.ac.jp/crid/1362544419242655616","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"The 2pπ*–3dπ interaction in aromatic silanes. Fluorescence from the 1(2pπ, 3dπ) intramolecular charge-transfer state"}]},{"@id":"https://cir.nii.ac.jp/crid/1362544419457653504","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Dual fluorescence of aryldisilanes and related compounds:  evidence for the formation of 1(.sigma..pi.*) orthogonal intramolecular charge-transfer states"}]},{"@id":"https://cir.nii.ac.jp/crid/1362544421188963584","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"OH stretching vibrations of phenol—(H2O)  (n=1–3) complexes observed by IR-UV double-resonance spectroscopy"}]},{"@id":"https://cir.nii.ac.jp/crid/1363107368422360064","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Infrared Vibrational Autodetachment Spectroscopy of Microsolvated Benzonitrile Radical Anions"}]},{"@id":"https://cir.nii.ac.jp/crid/1363107369268581376","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Intramolecular Charge-Transfer Process of Jet-Cooled (<i>p</i>-Cyanophenyl)pentamethyldisilane:  Roles of the Torsional Motion and the Si−Si Bond Change"}]},{"@id":"https://cir.nii.ac.jp/crid/1363107370355852672","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"First Observation of Intramolecular Charge-Transfer Emission from Jet-Cooled (<i>p</i>-Cyanophenyl)pentamethyldisilane in an Isolated Molecular Condition"}]},{"@id":"https://cir.nii.ac.jp/crid/1363107370493754880","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"IR-dip and IR–UV hole-burning spectra of jet-cooled 4-aminobenzonitrile–(H2O)1. Observation of π-type and σ-type hydrogen-bonded conformers in the CN site"}]},{"@id":"https://cir.nii.ac.jp/crid/1363388843681674240","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Vibrational Spectroscopy of the Cl<sup>-</sup>(H<sub>2</sub>O)<i><sub>n</sub></i> Anionic Clusters, <i>n</i> = 1−5"}]},{"@id":"https://cir.nii.ac.jp/crid/1363388844914592640","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Experimental and Theoretical Studies on the Intramolecular Charge-Transfer Emission of Phenyldisilanes"}]},{"@id":"https://cir.nii.ac.jp/crid/1363388845074830208","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Fluorescence from the intramolecular charge-transfer state of aromatic silanes"}]},{"@id":"https://cir.nii.ac.jp/crid/1363388845779629568","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Dipolmoment und Elektronenstruktur von angeregten Molekülen"}]},{"@id":"https://cir.nii.ac.jp/crid/1363670319501628160","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Rotational analysis of jet-cooled phenylpentamethyldisilane: vibronic interaction with the intramolecular charge-transfer state"}]},{"@id":"https://cir.nii.ac.jp/crid/1363670319768477184","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Determination of the Equilibrium Structure of the Charge-transfer State of (<i>p</i>-Cyanophenyl)pentamethyldisilane by Means of Transient Infrared Spectroscopy"}]},{"@id":"https://cir.nii.ac.jp/crid/1363670320458217856","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"OH Stretching Vibrations of Phenol−(H<sub>2</sub>O)<sub>1</sub> and Phenol−(H<sub>2</sub>O)<sub>3</sub> in the S<sub>1</sub> State"}]},{"@id":"https://cir.nii.ac.jp/crid/1363670321158580736","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Chemical reactions in isolated clusters: Excited state electron transfer in 3- and 4-dimethylaminobenzonitrile"}]}],"dataSourceIdentifier":[{"@type":"JALC","@value":"oai:japanlinkcenter.org:0031066167"},{"@type":"CROSSREF","@value":"10.3175/molsci.2.a0019"},{"@type":"CIA","@value":"130002126187"},{"@type":"CROSSREF","@value":"10.1016/j.jphotochem.2024.115465_references_DOI_5CuUt4nGdDkhIDU17oipIaprFd5"}]}