Synthesis and Spectroscopic Studies of Cyclometalated Pt(II) Complexes Containing a Functionalized Cyclometalating Ligand, 2-Phenyl-6-(1H-pyrazol-3-yl)-pyridine
Three new luminescent cyclometalated Pt(II) complexes, [Pt(L)Cl] (1), [Pt2(L-)2] (2), and [Pt(L)(PPh3)]ClO4 (3·ClO4) (where HL = 2-phenyl-6-(1H-pyrazol-3-yl)-pyridine), were synthesized and characterized by X-ray crystallography. HL represents a new class of C,N,Npyrazolyl cyclometalating ligands co...
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Veröffentlicht in: | Inorganic chemistry 2007-04, Vol.46 (9), p.3603-3612 |
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description | Three new luminescent cyclometalated Pt(II) complexes, [Pt(L)Cl] (1), [Pt2(L-)2] (2), and [Pt(L)(PPh3)]ClO4 (3·ClO4) (where HL = 2-phenyl-6-(1H-pyrazol-3-yl)-pyridine), were synthesized and characterized by X-ray crystallography. HL represents a new class of C,N,Npyrazolyl cyclometalating ligands containing a Cphenyl, a Npyridyl, and a Npyrazolyl donor moiety, as well as a 1-pyrazolyl-NH, that can also be available for metal coordination and other chemical interactions. Complex 1 possesses intense intraligand transitions at 275−375 nm and moderately intense metal-to-ligand charge transfer (1MLCT) (dπ(Pt) → π*(L)) transition at 380−410 nm. The room temperature solid-state emission λmax of 1 occurs at 580 nm and is attributable to the 3MMLCT (dσ*(Pt) → π*(L)) transition. It also displays strong phosphorescence in acetonitrile solutions at room temperature with an emission λmax at 514 nm, which can be tentatively assigned to the 3MLCT (π*(L) → dπ(Pt)) transition. Complex 1 can be deprotonated in organic solvents to yield a cycloplatinated dimer 2, which shows a relatively high room-temperature luminescent quantum yield of 0.59 in DMF (λmax = 509 nm). Substitution of the ancillary chloro-ligand in 1 by triphenylphosphine yields 3, which also possesses a good room-temperature luminescent quantum yield of 0.52 in DMF (λmax = 504 nm) and a better solubility in water. Complex 3 is synthesized to demonstrate the pH dependence of luminescent properties of this C,N,Npyrazolyl cyclometalated Pt(II) system. Such a pH response is ascribable to the protonation/deprotonation of the 1-pyrazolyl-NH on the C,N,Npyrazolyl cyclometalating ligand. The pK a of the 1-pyrazolyl-NH in 3, measured in 1:2 (v/v) aqueous DMF solutions, is approximately 4.0. |
doi_str_mv | 10.1021/ic062439j |
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HL represents a new class of C,N,Npyrazolyl cyclometalating ligands containing a Cphenyl, a Npyridyl, and a Npyrazolyl donor moiety, as well as a 1-pyrazolyl-NH, that can also be available for metal coordination and other chemical interactions. Complex 1 possesses intense intraligand transitions at 275−375 nm and moderately intense metal-to-ligand charge transfer (1MLCT) (dπ(Pt) → π*(L)) transition at 380−410 nm. The room temperature solid-state emission λmax of 1 occurs at 580 nm and is attributable to the 3MMLCT (dσ*(Pt) → π*(L)) transition. It also displays strong phosphorescence in acetonitrile solutions at room temperature with an emission λmax at 514 nm, which can be tentatively assigned to the 3MLCT (π*(L) → dπ(Pt)) transition. Complex 1 can be deprotonated in organic solvents to yield a cycloplatinated dimer 2, which shows a relatively high room-temperature luminescent quantum yield of 0.59 in DMF (λmax = 509 nm). Substitution of the ancillary chloro-ligand in 1 by triphenylphosphine yields 3, which also possesses a good room-temperature luminescent quantum yield of 0.52 in DMF (λmax = 504 nm) and a better solubility in water. Complex 3 is synthesized to demonstrate the pH dependence of luminescent properties of this C,N,Npyrazolyl cyclometalated Pt(II) system. Such a pH response is ascribable to the protonation/deprotonation of the 1-pyrazolyl-NH on the C,N,Npyrazolyl cyclometalating ligand. The pK a of the 1-pyrazolyl-NH in 3, measured in 1:2 (v/v) aqueous DMF solutions, is approximately 4.0.</description><identifier>ISSN: 0020-1669</identifier><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/ic062439j</identifier><identifier>PMID: 17408265</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Crystallography, X-Ray ; Cyclization ; Ligands ; Models, Molecular ; Molecular Structure ; Platinum Compounds - chemical synthesis ; Platinum Compounds - chemistry ; Pyrazoles - chemistry ; Pyridines - chemistry ; Solutions ; Spectrum Analysis ; Temperature</subject><ispartof>Inorganic chemistry, 2007-04, Vol.46 (9), p.3603-3612</ispartof><rights>Copyright © 2007 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a417t-912a0c5b5352fe95de250827c9e729cf5d3f6dc5d02a7362b750e1c724d14a123</citedby><cites>FETCH-LOGICAL-a417t-912a0c5b5352fe95de250827c9e729cf5d3f6dc5d02a7362b750e1c724d14a123</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ic062439j$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ic062439j$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>315,781,785,2766,27081,27929,27930,56743,56793</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/17408265$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Koo, Chi-Kin</creatorcontrib><creatorcontrib>Ho, Yu-Man</creatorcontrib><creatorcontrib>Chow, Cheuk-Fai</creatorcontrib><creatorcontrib>Lam, Michael Hon-Wah</creatorcontrib><creatorcontrib>Lau, Tai-Chu</creatorcontrib><creatorcontrib>Wong, Wai-Yeung</creatorcontrib><title>Synthesis and Spectroscopic Studies of Cyclometalated Pt(II) Complexes Containing a Functionalized Cyclometalating Ligand, 2-Phenyl-6-(1H-pyrazol-3-yl)-pyridine</title><title>Inorganic chemistry</title><addtitle>Inorg. Chem</addtitle><description>Three new luminescent cyclometalated Pt(II) complexes, [Pt(L)Cl] (1), [Pt2(L-)2] (2), and [Pt(L)(PPh3)]ClO4 (3·ClO4) (where HL = 2-phenyl-6-(1H-pyrazol-3-yl)-pyridine), were synthesized and characterized by X-ray crystallography. HL represents a new class of C,N,Npyrazolyl cyclometalating ligands containing a Cphenyl, a Npyridyl, and a Npyrazolyl donor moiety, as well as a 1-pyrazolyl-NH, that can also be available for metal coordination and other chemical interactions. Complex 1 possesses intense intraligand transitions at 275−375 nm and moderately intense metal-to-ligand charge transfer (1MLCT) (dπ(Pt) → π*(L)) transition at 380−410 nm. The room temperature solid-state emission λmax of 1 occurs at 580 nm and is attributable to the 3MMLCT (dσ*(Pt) → π*(L)) transition. It also displays strong phosphorescence in acetonitrile solutions at room temperature with an emission λmax at 514 nm, which can be tentatively assigned to the 3MLCT (π*(L) → dπ(Pt)) transition. Complex 1 can be deprotonated in organic solvents to yield a cycloplatinated dimer 2, which shows a relatively high room-temperature luminescent quantum yield of 0.59 in DMF (λmax = 509 nm). Substitution of the ancillary chloro-ligand in 1 by triphenylphosphine yields 3, which also possesses a good room-temperature luminescent quantum yield of 0.52 in DMF (λmax = 504 nm) and a better solubility in water. Complex 3 is synthesized to demonstrate the pH dependence of luminescent properties of this C,N,Npyrazolyl cyclometalated Pt(II) system. Such a pH response is ascribable to the protonation/deprotonation of the 1-pyrazolyl-NH on the C,N,Npyrazolyl cyclometalating ligand. The pK a of the 1-pyrazolyl-NH in 3, measured in 1:2 (v/v) aqueous DMF solutions, is approximately 4.0.</description><subject>Crystallography, X-Ray</subject><subject>Cyclization</subject><subject>Ligands</subject><subject>Models, Molecular</subject><subject>Molecular Structure</subject><subject>Platinum Compounds - chemical synthesis</subject><subject>Platinum Compounds - chemistry</subject><subject>Pyrazoles - chemistry</subject><subject>Pyridines - chemistry</subject><subject>Solutions</subject><subject>Spectrum Analysis</subject><subject>Temperature</subject><issn>0020-1669</issn><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2007</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpt0UGPEyEUB3BiNG5dPfgFDBfNNhEFZhh2jjpxt401Npma7I1QYHapFMaBSXb20_hRpWmzevAEhB_vhf8D4DXBHwim5KNVuKJlUe-egBlhFCNG8M1TMMM470lV1WfgRYw7jHFdlNVzcEZ4iS9pxWbgdzv5dGeijVB6DdveqDSEqEJvFWzTqK2JMHSwmZQLe5Okk8louE4Xy-UcNmHfO3OfSRN8ktZbfwslvBq9SjZ46exDxv--PYCVvc293kOK1nfGTw5V6IIsUD8N8iE4VKDJzQ8nq603L8GzTrpoXp3Wc_Dj6sumWaDV9-tl82mFZEl4QjWhEiu2ZQWjnamZNpTlL3JVG05r1TFddJVWTGMqeVHRLWfYEMVpqUkpCS3Owbtj3X4Iv0YTk9jbqIxz0pswRsFxSXFZXmY4P0KVc4qD6UQ_2L0cJkGwOIxDPI4j2zenouN2b_Rfeco_A3QENiZz_3gvh5-i4gVnYrNuxfW3xab9vL4RX7N_e_RSRbEL45Azjv9p_AejLqG3</recordid><startdate>20070430</startdate><enddate>20070430</enddate><creator>Koo, Chi-Kin</creator><creator>Ho, Yu-Man</creator><creator>Chow, Cheuk-Fai</creator><creator>Lam, Michael Hon-Wah</creator><creator>Lau, Tai-Chu</creator><creator>Wong, Wai-Yeung</creator><general>American Chemical Society</general><scope>BSCLL</scope><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>20070430</creationdate><title>Synthesis and Spectroscopic Studies of Cyclometalated Pt(II) Complexes Containing a Functionalized Cyclometalating Ligand, 2-Phenyl-6-(1H-pyrazol-3-yl)-pyridine</title><author>Koo, Chi-Kin ; Ho, Yu-Man ; Chow, Cheuk-Fai ; Lam, Michael Hon-Wah ; Lau, Tai-Chu ; Wong, Wai-Yeung</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a417t-912a0c5b5352fe95de250827c9e729cf5d3f6dc5d02a7362b750e1c724d14a123</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2007</creationdate><topic>Crystallography, X-Ray</topic><topic>Cyclization</topic><topic>Ligands</topic><topic>Models, Molecular</topic><topic>Molecular Structure</topic><topic>Platinum Compounds - chemical synthesis</topic><topic>Platinum Compounds - chemistry</topic><topic>Pyrazoles - chemistry</topic><topic>Pyridines - chemistry</topic><topic>Solutions</topic><topic>Spectrum Analysis</topic><topic>Temperature</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Koo, Chi-Kin</creatorcontrib><creatorcontrib>Ho, Yu-Man</creatorcontrib><creatorcontrib>Chow, Cheuk-Fai</creatorcontrib><creatorcontrib>Lam, Michael Hon-Wah</creatorcontrib><creatorcontrib>Lau, Tai-Chu</creatorcontrib><creatorcontrib>Wong, Wai-Yeung</creatorcontrib><collection>Istex</collection><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>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Koo, Chi-Kin</au><au>Ho, Yu-Man</au><au>Chow, Cheuk-Fai</au><au>Lam, Michael Hon-Wah</au><au>Lau, Tai-Chu</au><au>Wong, Wai-Yeung</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and Spectroscopic Studies of Cyclometalated Pt(II) Complexes Containing a Functionalized Cyclometalating Ligand, 2-Phenyl-6-(1H-pyrazol-3-yl)-pyridine</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg. Chem</addtitle><date>2007-04-30</date><risdate>2007</risdate><volume>46</volume><issue>9</issue><spage>3603</spage><epage>3612</epage><pages>3603-3612</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><abstract>Three new luminescent cyclometalated Pt(II) complexes, [Pt(L)Cl] (1), [Pt2(L-)2] (2), and [Pt(L)(PPh3)]ClO4 (3·ClO4) (where HL = 2-phenyl-6-(1H-pyrazol-3-yl)-pyridine), were synthesized and characterized by X-ray crystallography. HL represents a new class of C,N,Npyrazolyl cyclometalating ligands containing a Cphenyl, a Npyridyl, and a Npyrazolyl donor moiety, as well as a 1-pyrazolyl-NH, that can also be available for metal coordination and other chemical interactions. Complex 1 possesses intense intraligand transitions at 275−375 nm and moderately intense metal-to-ligand charge transfer (1MLCT) (dπ(Pt) → π*(L)) transition at 380−410 nm. The room temperature solid-state emission λmax of 1 occurs at 580 nm and is attributable to the 3MMLCT (dσ*(Pt) → π*(L)) transition. It also displays strong phosphorescence in acetonitrile solutions at room temperature with an emission λmax at 514 nm, which can be tentatively assigned to the 3MLCT (π*(L) → dπ(Pt)) transition. Complex 1 can be deprotonated in organic solvents to yield a cycloplatinated dimer 2, which shows a relatively high room-temperature luminescent quantum yield of 0.59 in DMF (λmax = 509 nm). Substitution of the ancillary chloro-ligand in 1 by triphenylphosphine yields 3, which also possesses a good room-temperature luminescent quantum yield of 0.52 in DMF (λmax = 504 nm) and a better solubility in water. Complex 3 is synthesized to demonstrate the pH dependence of luminescent properties of this C,N,Npyrazolyl cyclometalated Pt(II) system. Such a pH response is ascribable to the protonation/deprotonation of the 1-pyrazolyl-NH on the C,N,Npyrazolyl cyclometalating ligand. The pK a of the 1-pyrazolyl-NH in 3, measured in 1:2 (v/v) aqueous DMF solutions, is approximately 4.0.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>17408265</pmid><doi>10.1021/ic062439j</doi><tpages>10</tpages></addata></record> |
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subjects | Crystallography, X-Ray Cyclization Ligands Models, Molecular Molecular Structure Platinum Compounds - chemical synthesis Platinum Compounds - chemistry Pyrazoles - chemistry Pyridines - chemistry Solutions Spectrum Analysis Temperature |
title | Synthesis and Spectroscopic Studies of Cyclometalated Pt(II) Complexes Containing a Functionalized Cyclometalating Ligand, 2-Phenyl-6-(1H-pyrazol-3-yl)-pyridine |
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