Luminescent Pt(2,6-bis(-methylbenzimidazol-2-yl)pyridine)X: a comparison with the spectroscopic and electrochemical properties of Pt(tpy)X (X = Cl, CCPh, Ph, or CH)
A series of platinum( ii ) pincer complexes of the formula Pt(mbzimpy)X + , 1(a-d) , (mbzimpy = 2,6-bis( N -methylbenzimidazol-2-yl)pyridine; X = Cl; ( a ), CCPh; ( b ), Ph; ( c ), or CH 3 ; ( d ), CCPh = phenylacetylide, and Ph = Phenyl) have been synthesized and characterized. Electronic absorptio...
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| creator | Shingade, Vikas M Grove, Levi J Connick, William B |
| description | A series of platinum(
ii
) pincer complexes of the formula Pt(mbzimpy)X
+
,
1(a-d)
, (mbzimpy = 2,6-bis(
N
-methylbenzimidazol-2-yl)pyridine; X = Cl; (
a
), CCPh; (
b
), Ph; (
c
), or CH
3
; (
d
), CCPh = phenylacetylide, and Ph = Phenyl) have been synthesized and characterized. Electronic absorption and emission, as well as electrochemical properties of these compounds, have been investigated. Pt(tpy)X
+
analogs (tpy = 2,2′;6′2′′-terpyridine),
2
(a-d), have also been investigated and compared. Electrochemistry shows that
1
and
2
analogs undergo two chemically reversible one-electron reduction processes that are shifted cathodically along the a < b < c < d series. Notably, these reductions occur at slightly higher negative potentials in the case of
1
. The absorption spectra of
1
and
2
in acetonitrile exhibit ligand-centered (
1
LC) transitions (
10
4
M
−1
cm
−1
) in the UV region and metal-to-ligand-charge transfer (
1
MLCT) transitions (
10
3
M
−1
cm
−1
) in the visible region. The corresponding visible bands of
1b
and
2b
have been assigned to
1
(LLCT/MLCT) mixed state (LLCT: ligand-to-ligand-charge transfer). The preceding
1
LC and
1
MLCT transitions of
1
occur at lower energies than that of
2
. These
1
LC transitions have distinctly been blue-shifted along a < c < d in
2
, but occur at nearly identical energies in
1
. Conversely,
1
MLCT transitions are red-shifted along a < c < d in both the analogs. The 77 K glassy solutions of
1
and
2
exhibit an intense vibronically-structured emission band at
λ
max
(0-0) in the 470-560 nm range. This band is red-shifted along b < a ≤ c < d in
1
and along a ≤ d c < b in
2
. The main character of these emissions is assigned to
3
LLCT emissive state in
1b
and
2b
, whereas to
3
LC in the rest of the compounds. Relative stabilization of these spin-forbidden emissive states is discussed by invoking configuration mixing with the higher-lying
3
MLCT state.
Spectroscopic and electrochemical properties of photoluminescent Pt(2,6-bis(
N
-methylbenzimidazol-2-yl)pyridine)X
+
have been discussed and contrasted with that of the archetypal Pt(tpy)X
+
for better understanding of their electronic structures. |
| doi_str_mv | 10.1039/d0dt01496f |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_rsc_p</sourceid><recordid>TN_cdi_proquest_journals_2425518548</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2425518548</sourcerecordid><originalsourceid>FETCH-LOGICAL-c340t-dbc685f88acd481ea70dd1130a8bab457763ab45626be5e5f415b244e57116ef3</originalsourceid><addsrcrecordid>eNp9kU1r3DAQhk1poGnSS-8FlV52y7rVp-0t5FCcpiksNIcU9mZkaYwVZEuVtATn9_SH1s6WFHroYZhh5pkP5s2y1wR_IJhtP2qsEyZ8W3TPslPCyzLfUsafP8W0eJG9jPEOY0qxoKfZr91hMCNEBWNCN2lFN0XemrjKB0j9ZFsYH8xgtHxwNqf5ZNd-CkbPHev9JySRcoOXwUQ3onuTepR6QNGDSsFF5bxRSI4agX3MqB4Go6RFPjgPIRmIyHXL1uSn9R6t9ugC1XaD6vqm36DFXED19fo8O-mkjfDqjz_Lflx9ua2v8933r9_qz7tcMY5TrltVVKKrKqk0rwjIEmtNCMOyamXLRVkWbPEFLVoQIDpOREs5B1ESUkDHzrLVce584M8DxNQMZv6MtXIEd4gN5RQXjDG-ndF3_6B37hDG-bqFEoJUglcz9f5IqfkfMUDX-GAGGaaG4GYRrLnEl7ePgl3N8JsjHKJ64v4KOtff_q_eeN2x37rNnLc</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2425518548</pqid></control><display><type>article</type><title>Luminescent Pt(2,6-bis(-methylbenzimidazol-2-yl)pyridine)X: a comparison with the spectroscopic and electrochemical properties of Pt(tpy)X (X = Cl, CCPh, Ph, or CH)</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Shingade, Vikas M ; Grove, Levi J ; Connick, William B</creator><creatorcontrib>Shingade, Vikas M ; Grove, Levi J ; Connick, William B</creatorcontrib><description><![CDATA[A series of platinum(
ii
) pincer complexes of the formula Pt(mbzimpy)X
+
,
1(a-d)
, (mbzimpy = 2,6-bis(
N
-methylbenzimidazol-2-yl)pyridine; X = Cl; (
a
), CCPh; (
b
), Ph; (
c
), or CH
3
; (
d
), CCPh = phenylacetylide, and Ph = Phenyl) have been synthesized and characterized. Electronic absorption and emission, as well as electrochemical properties of these compounds, have been investigated. Pt(tpy)X
+
analogs (tpy = 2,2′;6′2′′-terpyridine),
2
(a-d), have also been investigated and compared. Electrochemistry shows that
1
and
2
analogs undergo two chemically reversible one-electron reduction processes that are shifted cathodically along the a < b < c < d series. Notably, these reductions occur at slightly higher negative potentials in the case of
1
. The absorption spectra of
1
and
2
in acetonitrile exhibit ligand-centered (
1
LC) transitions (
10
4
M
−1
cm
−1
) in the UV region and metal-to-ligand-charge transfer (
1
MLCT) transitions (
10
3
M
−1
cm
−1
) in the visible region. The corresponding visible bands of
1b
and
2b
have been assigned to
1
(LLCT/MLCT) mixed state (LLCT: ligand-to-ligand-charge transfer). The preceding
1
LC and
1
MLCT transitions of
1
occur at lower energies than that of
2
. These
1
LC transitions have distinctly been blue-shifted along a < c < d in
2
, but occur at nearly identical energies in
1
. Conversely,
1
MLCT transitions are red-shifted along a < c < d in both the analogs. The 77 K glassy solutions of
1
and
2
exhibit an intense vibronically-structured emission band at
λ
max
(0-0) in the 470-560 nm range. This band is red-shifted along b < a ≤ c < d in
1
and along a ≤ d c < b in
2
. The main character of these emissions is assigned to
3
LLCT emissive state in
1b
and
2b
, whereas to
3
LC in the rest of the compounds. Relative stabilization of these spin-forbidden emissive states is discussed by invoking configuration mixing with the higher-lying
3
MLCT state.
Spectroscopic and electrochemical properties of photoluminescent Pt(2,6-bis(
N
-methylbenzimidazol-2-yl)pyridine)X
+
have been discussed and contrasted with that of the archetypal Pt(tpy)X
+
for better understanding of their electronic structures.]]></description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/d0dt01496f</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Absorption spectra ; Acetonitrile ; Analogs ; Blue shift ; Charge transfer ; Electrochemical analysis ; Electrochemistry ; Emission analysis ; Emission spectra ; Excitation spectra ; Ligands ; NMR ; Nuclear magnetic resonance ; Platinum</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2020-07, Vol.49 (28), p.9651-9661</ispartof><rights>Copyright Royal Society of Chemistry 2020</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c340t-dbc685f88acd481ea70dd1130a8bab457763ab45626be5e5f415b244e57116ef3</citedby><cites>FETCH-LOGICAL-c340t-dbc685f88acd481ea70dd1130a8bab457763ab45626be5e5f415b244e57116ef3</cites><orcidid>0000-0001-9888-151X</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Shingade, Vikas M</creatorcontrib><creatorcontrib>Grove, Levi J</creatorcontrib><creatorcontrib>Connick, William B</creatorcontrib><title>Luminescent Pt(2,6-bis(-methylbenzimidazol-2-yl)pyridine)X: a comparison with the spectroscopic and electrochemical properties of Pt(tpy)X (X = Cl, CCPh, Ph, or CH)</title><title>Dalton transactions : an international journal of inorganic chemistry</title><description><![CDATA[A series of platinum(
ii
) pincer complexes of the formula Pt(mbzimpy)X
+
,
1(a-d)
, (mbzimpy = 2,6-bis(
N
-methylbenzimidazol-2-yl)pyridine; X = Cl; (
a
), CCPh; (
b
), Ph; (
c
), or CH
3
; (
d
), CCPh = phenylacetylide, and Ph = Phenyl) have been synthesized and characterized. Electronic absorption and emission, as well as electrochemical properties of these compounds, have been investigated. Pt(tpy)X
+
analogs (tpy = 2,2′;6′2′′-terpyridine),
2
(a-d), have also been investigated and compared. Electrochemistry shows that
1
and
2
analogs undergo two chemically reversible one-electron reduction processes that are shifted cathodically along the a < b < c < d series. Notably, these reductions occur at slightly higher negative potentials in the case of
1
. The absorption spectra of
1
and
2
in acetonitrile exhibit ligand-centered (
1
LC) transitions (
10
4
M
−1
cm
−1
) in the UV region and metal-to-ligand-charge transfer (
1
MLCT) transitions (
10
3
M
−1
cm
−1
) in the visible region. The corresponding visible bands of
1b
and
2b
have been assigned to
1
(LLCT/MLCT) mixed state (LLCT: ligand-to-ligand-charge transfer). The preceding
1
LC and
1
MLCT transitions of
1
occur at lower energies than that of
2
. These
1
LC transitions have distinctly been blue-shifted along a < c < d in
2
, but occur at nearly identical energies in
1
. Conversely,
1
MLCT transitions are red-shifted along a < c < d in both the analogs. The 77 K glassy solutions of
1
and
2
exhibit an intense vibronically-structured emission band at
λ
max
(0-0) in the 470-560 nm range. This band is red-shifted along b < a ≤ c < d in
1
and along a ≤ d c < b in
2
. The main character of these emissions is assigned to
3
LLCT emissive state in
1b
and
2b
, whereas to
3
LC in the rest of the compounds. Relative stabilization of these spin-forbidden emissive states is discussed by invoking configuration mixing with the higher-lying
3
MLCT state.
Spectroscopic and electrochemical properties of photoluminescent Pt(2,6-bis(
N
-methylbenzimidazol-2-yl)pyridine)X
+
have been discussed and contrasted with that of the archetypal Pt(tpy)X
+
for better understanding of their electronic structures.]]></description><subject>Absorption spectra</subject><subject>Acetonitrile</subject><subject>Analogs</subject><subject>Blue shift</subject><subject>Charge transfer</subject><subject>Electrochemical analysis</subject><subject>Electrochemistry</subject><subject>Emission analysis</subject><subject>Emission spectra</subject><subject>Excitation spectra</subject><subject>Ligands</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Platinum</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNp9kU1r3DAQhk1poGnSS-8FlV52y7rVp-0t5FCcpiksNIcU9mZkaYwVZEuVtATn9_SH1s6WFHroYZhh5pkP5s2y1wR_IJhtP2qsEyZ8W3TPslPCyzLfUsafP8W0eJG9jPEOY0qxoKfZr91hMCNEBWNCN2lFN0XemrjKB0j9ZFsYH8xgtHxwNqf5ZNd-CkbPHev9JySRcoOXwUQ3onuTepR6QNGDSsFF5bxRSI4agX3MqB4Go6RFPjgPIRmIyHXL1uSn9R6t9ugC1XaD6vqm36DFXED19fo8O-mkjfDqjz_Lflx9ua2v8933r9_qz7tcMY5TrltVVKKrKqk0rwjIEmtNCMOyamXLRVkWbPEFLVoQIDpOREs5B1ESUkDHzrLVce584M8DxNQMZv6MtXIEd4gN5RQXjDG-ndF3_6B37hDG-bqFEoJUglcz9f5IqfkfMUDX-GAGGaaG4GYRrLnEl7ePgl3N8JsjHKJ64v4KOtff_q_eeN2x37rNnLc</recordid><startdate>20200721</startdate><enddate>20200721</enddate><creator>Shingade, Vikas M</creator><creator>Grove, Levi J</creator><creator>Connick, William B</creator><general>Royal Society of Chemistry</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0001-9888-151X</orcidid></search><sort><creationdate>20200721</creationdate><title>Luminescent Pt(2,6-bis(-methylbenzimidazol-2-yl)pyridine)X: a comparison with the spectroscopic and electrochemical properties of Pt(tpy)X (X = Cl, CCPh, Ph, or CH)</title><author>Shingade, Vikas M ; Grove, Levi J ; Connick, William B</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c340t-dbc685f88acd481ea70dd1130a8bab457763ab45626be5e5f415b244e57116ef3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Absorption spectra</topic><topic>Acetonitrile</topic><topic>Analogs</topic><topic>Blue shift</topic><topic>Charge transfer</topic><topic>Electrochemical analysis</topic><topic>Electrochemistry</topic><topic>Emission analysis</topic><topic>Emission spectra</topic><topic>Excitation spectra</topic><topic>Ligands</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Platinum</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Shingade, Vikas M</creatorcontrib><creatorcontrib>Grove, Levi J</creatorcontrib><creatorcontrib>Connick, William B</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Shingade, Vikas M</au><au>Grove, Levi J</au><au>Connick, William B</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Luminescent Pt(2,6-bis(-methylbenzimidazol-2-yl)pyridine)X: a comparison with the spectroscopic and electrochemical properties of Pt(tpy)X (X = Cl, CCPh, Ph, or CH)</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><date>2020-07-21</date><risdate>2020</risdate><volume>49</volume><issue>28</issue><spage>9651</spage><epage>9661</epage><pages>9651-9661</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract><![CDATA[A series of platinum(
ii
) pincer complexes of the formula Pt(mbzimpy)X
+
,
1(a-d)
, (mbzimpy = 2,6-bis(
N
-methylbenzimidazol-2-yl)pyridine; X = Cl; (
a
), CCPh; (
b
), Ph; (
c
), or CH
3
; (
d
), CCPh = phenylacetylide, and Ph = Phenyl) have been synthesized and characterized. Electronic absorption and emission, as well as electrochemical properties of these compounds, have been investigated. Pt(tpy)X
+
analogs (tpy = 2,2′;6′2′′-terpyridine),
2
(a-d), have also been investigated and compared. Electrochemistry shows that
1
and
2
analogs undergo two chemically reversible one-electron reduction processes that are shifted cathodically along the a < b < c < d series. Notably, these reductions occur at slightly higher negative potentials in the case of
1
. The absorption spectra of
1
and
2
in acetonitrile exhibit ligand-centered (
1
LC) transitions (
10
4
M
−1
cm
−1
) in the UV region and metal-to-ligand-charge transfer (
1
MLCT) transitions (
10
3
M
−1
cm
−1
) in the visible region. The corresponding visible bands of
1b
and
2b
have been assigned to
1
(LLCT/MLCT) mixed state (LLCT: ligand-to-ligand-charge transfer). The preceding
1
LC and
1
MLCT transitions of
1
occur at lower energies than that of
2
. These
1
LC transitions have distinctly been blue-shifted along a < c < d in
2
, but occur at nearly identical energies in
1
. Conversely,
1
MLCT transitions are red-shifted along a < c < d in both the analogs. The 77 K glassy solutions of
1
and
2
exhibit an intense vibronically-structured emission band at
λ
max
(0-0) in the 470-560 nm range. This band is red-shifted along b < a ≤ c < d in
1
and along a ≤ d c < b in
2
. The main character of these emissions is assigned to
3
LLCT emissive state in
1b
and
2b
, whereas to
3
LC in the rest of the compounds. Relative stabilization of these spin-forbidden emissive states is discussed by invoking configuration mixing with the higher-lying
3
MLCT state.
Spectroscopic and electrochemical properties of photoluminescent Pt(2,6-bis(
N
-methylbenzimidazol-2-yl)pyridine)X
+
have been discussed and contrasted with that of the archetypal Pt(tpy)X
+
for better understanding of their electronic structures.]]></abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d0dt01496f</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0001-9888-151X</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-9226 |
| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2020-07, Vol.49 (28), p.9651-9661 |
| issn | 1477-9226 1477-9234 |
| language | eng |
| recordid | cdi_proquest_journals_2425518548 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Absorption spectra Acetonitrile Analogs Blue shift Charge transfer Electrochemical analysis Electrochemistry Emission analysis Emission spectra Excitation spectra Ligands NMR Nuclear magnetic resonance Platinum |
| title | Luminescent Pt(2,6-bis(-methylbenzimidazol-2-yl)pyridine)X: a comparison with the spectroscopic and electrochemical properties of Pt(tpy)X (X = Cl, CCPh, Ph, or CH) |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-20T17%3A02%3A40IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_rsc_p&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Luminescent%20Pt(2,6-bis(-methylbenzimidazol-2-yl)pyridine)X:%20a%20comparison%20with%20the%20spectroscopic%20and%20electrochemical%20properties%20of%20Pt(tpy)X%20(X%20=%20Cl,%20CCPh,%20Ph,%20or%20CH)&rft.jtitle=Dalton%20transactions%20:%20an%20international%20journal%20of%20inorganic%20chemistry&rft.au=Shingade,%20Vikas%20M&rft.date=2020-07-21&rft.volume=49&rft.issue=28&rft.spage=9651&rft.epage=9661&rft.pages=9651-9661&rft.issn=1477-9226&rft.eissn=1477-9234&rft_id=info:doi/10.1039/d0dt01496f&rft_dat=%3Cproquest_rsc_p%3E2425518548%3C/proquest_rsc_p%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=2425518548&rft_id=info:pmid/&rfr_iscdi=true |