Photophysical Studies of trans-Bis(phenylethynyldiisopropylamidinato)bis(acetato)dimetal Complexes Involving MM Quadruple Bonds Where M = Mo or W
The title compounds trans-M2(O2CMe)2[C( i PrN)2CCPh]2, I (M = Mo) and II (M = W), show electronic absorptions in the visible region of the spectrum assignable to 1MLCT [M2δ to phenylethynylamidinate π*]. These compounds show dual emission from S1 and T1 states. For both I and II, S1 is 1MLCT, but...
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| Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2010-12, Vol.114 (48), p.12675-12681 |
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| container_issue | 48 |
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| container_title | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory |
| container_volume | 114 |
| creator | Alberding, Brian G Chisholm, Malcolm H Gustafson, Terry L Liu, Yao Reed, Carly R Turro, Claudia |
| description | The title compounds trans-M2(O2CMe)2[C( i PrN)2CCPh]2, I (M = Mo) and II (M = W), show electronic absorptions in the visible region of the spectrum assignable to 1MLCT [M2δ to phenylethynylamidinate π*]. These compounds show dual emission from S1 and T1 states. For both I and II, S1 is 1MLCT, but for I the T1 state is shown to be MMδδ* while for II T1 is 3MLCT. The lifetimes of the S1 and T1 states have been determined by femtosecond and nanosecond transient absorption spectroscopy: for I S1 ∼ 20 ps and T1 ∼ 100 μs and for II S1 ∼ 6 ps and T1 ∼ 5 μs. From solvent dependence of the absorption and emission spectra, we suggest that the S1 states are localized on one amidinate ligand though the initial absorption is to a delocalized state. |
| doi_str_mv | 10.1021/jp108544v |
| format | Article |
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These compounds show dual emission from S1 and T1 states. For both I and II, S1 is 1MLCT, but for I the T1 state is shown to be MMδδ* while for II T1 is 3MLCT. The lifetimes of the S1 and T1 states have been determined by femtosecond and nanosecond transient absorption spectroscopy: for I S1 ∼ 20 ps and T1 ∼ 100 μs and for II S1 ∼ 6 ps and T1 ∼ 5 μs. From solvent dependence of the absorption and emission spectra, we suggest that the S1 states are localized on one amidinate ligand though the initial absorption is to a delocalized state.</description><identifier>ISSN: 1089-5639</identifier><identifier>EISSN: 1520-5215</identifier><identifier>DOI: 10.1021/jp108544v</identifier><identifier>PMID: 21067133</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>A: Kinetics, Spectroscopy ; Alkynes - chemistry ; Amidines - chemistry ; Models, Molecular ; Molybdenum - chemistry ; Organometallic Compounds - chemistry ; Photochemistry ; Quantum Theory ; Tungsten - chemistry</subject><ispartof>The journal of physical chemistry. 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A, Molecules, spectroscopy, kinetics, environment, & general theory</title><addtitle>J. Phys. Chem. A</addtitle><description>The title compounds trans-M2(O2CMe)2[C( i PrN)2CCPh]2, I (M = Mo) and II (M = W), show electronic absorptions in the visible region of the spectrum assignable to 1MLCT [M2δ to phenylethynylamidinate π*]. These compounds show dual emission from S1 and T1 states. For both I and II, S1 is 1MLCT, but for I the T1 state is shown to be MMδδ* while for II T1 is 3MLCT. The lifetimes of the S1 and T1 states have been determined by femtosecond and nanosecond transient absorption spectroscopy: for I S1 ∼ 20 ps and T1 ∼ 100 μs and for II S1 ∼ 6 ps and T1 ∼ 5 μs. From solvent dependence of the absorption and emission spectra, we suggest that the S1 states are localized on one amidinate ligand though the initial absorption is to a delocalized state.</description><subject>A: Kinetics, Spectroscopy</subject><subject>Alkynes - chemistry</subject><subject>Amidines - chemistry</subject><subject>Models, Molecular</subject><subject>Molybdenum - chemistry</subject><subject>Organometallic Compounds - chemistry</subject><subject>Photochemistry</subject><subject>Quantum Theory</subject><subject>Tungsten - chemistry</subject><issn>1089-5639</issn><issn>1520-5215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkc1O3DAUhS1UxAzQRV-g8qYCFqG-cX4XLMqIP2lGpWorlpET3zQeOXFqJyPyGLwxHg3MitU5uvfTkc69hHwBdgkshO_rHlgWR9HmgMwhDlkQhxB_8p5leRAnPJ-RY-fWjDHgYXREZiGwJAXO5-TlsTGD6ZvJqUpo-nsYpUJHTU0HKzoXXCt33jfYTRqHZvIilXKmt6aftGiVVJ0YzEXpKVHhsPVStd5oujBtr_HZhz10G6M3qvtHVyv6axTSjn5Dr00nHX1q0CJd0Su6MtRY-nRKDmuhHX5-0xPy9_bmz-I-WP68e1j8WAaCQzQEKLEOBUAZJWWV5Zhxvh2EZcRBJFLWZZWCkJyxOBGh35UZSyCv8zQqRYzIT8jZLteX-T-iG4pWuQq1Fh2a0RUZxHmSspR58mJHVtY4Z7EueqtaYacCWLF9QLF_gGe_vqWOZYtyT75f3APfdoCoXLE2o-18yQ-CXgHpmpBU</recordid><startdate>20101209</startdate><enddate>20101209</enddate><creator>Alberding, Brian G</creator><creator>Chisholm, Malcolm H</creator><creator>Gustafson, Terry L</creator><creator>Liu, Yao</creator><creator>Reed, Carly R</creator><creator>Turro, Claudia</creator><general>American Chemical Society</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20101209</creationdate><title>Photophysical Studies of trans-Bis(phenylethynyldiisopropylamidinato)bis(acetato)dimetal Complexes Involving MM Quadruple Bonds Where M = Mo or W</title><author>Alberding, Brian G ; Chisholm, Malcolm H ; Gustafson, Terry L ; Liu, Yao ; Reed, Carly R ; Turro, Claudia</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a314t-edef2a11b46bc89e833ef2a2b431a6ddfbc71ad30056a23efb80619f974ba5ee3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><topic>A: Kinetics, Spectroscopy</topic><topic>Alkynes - chemistry</topic><topic>Amidines - chemistry</topic><topic>Models, Molecular</topic><topic>Molybdenum - chemistry</topic><topic>Organometallic Compounds - chemistry</topic><topic>Photochemistry</topic><topic>Quantum Theory</topic><topic>Tungsten - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Alberding, Brian G</creatorcontrib><creatorcontrib>Chisholm, Malcolm H</creatorcontrib><creatorcontrib>Gustafson, Terry L</creatorcontrib><creatorcontrib>Liu, Yao</creatorcontrib><creatorcontrib>Reed, Carly R</creatorcontrib><creatorcontrib>Turro, Claudia</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Alberding, Brian G</au><au>Chisholm, Malcolm H</au><au>Gustafson, Terry L</au><au>Liu, Yao</au><au>Reed, Carly R</au><au>Turro, Claudia</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Photophysical Studies of trans-Bis(phenylethynyldiisopropylamidinato)bis(acetato)dimetal Complexes Involving MM Quadruple Bonds Where M = Mo or W</atitle><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle><addtitle>J. Phys. Chem. A</addtitle><date>2010-12-09</date><risdate>2010</risdate><volume>114</volume><issue>48</issue><spage>12675</spage><epage>12681</epage><pages>12675-12681</pages><issn>1089-5639</issn><eissn>1520-5215</eissn><abstract>The title compounds trans-M2(O2CMe)2[C( i PrN)2CCPh]2, I (M = Mo) and II (M = W), show electronic absorptions in the visible region of the spectrum assignable to 1MLCT [M2δ to phenylethynylamidinate π*]. These compounds show dual emission from S1 and T1 states. For both I and II, S1 is 1MLCT, but for I the T1 state is shown to be MMδδ* while for II T1 is 3MLCT. The lifetimes of the S1 and T1 states have been determined by femtosecond and nanosecond transient absorption spectroscopy: for I S1 ∼ 20 ps and T1 ∼ 100 μs and for II S1 ∼ 6 ps and T1 ∼ 5 μs. From solvent dependence of the absorption and emission spectra, we suggest that the S1 states are localized on one amidinate ligand though the initial absorption is to a delocalized state.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>21067133</pmid><doi>10.1021/jp108544v</doi><tpages>7</tpages></addata></record> |
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| ispartof | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2010-12, Vol.114 (48), p.12675-12681 |
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| source | MEDLINE; ACS Publications |
| subjects | A: Kinetics, Spectroscopy Alkynes - chemistry Amidines - chemistry Models, Molecular Molybdenum - chemistry Organometallic Compounds - chemistry Photochemistry Quantum Theory Tungsten - chemistry |
| title | Photophysical Studies of trans-Bis(phenylethynyldiisopropylamidinato)bis(acetato)dimetal Complexes Involving MM Quadruple Bonds Where M = Mo or W |
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