Synthesis, crystal structures, photophysical, electrochemical studies, DFT and TD-DFT calculations and Hirshfeld analysis of new 2,2′:6′,2′′-terpyridine ligands with pendant 4′-(trimethoxyphenyl) groups and their homoleptic ruthenium complexes
Two new ligands, 4′-(2,3,4-trimethoxyphenyl)-2,2′:6′,2′′-terpyridine ( L 1 ) and 4′(2,4,5-trimethoxyphenyl)-2,2′:6′,2′′-terpyridine ( L 2 ), and their homoleptic ruthenium( ii ) complexes, [Ru( L 1 ) 2 ](PF 6 ) 2 ( 1 ) and [Ru( L 2 ) 2 ](PF 6 ) 2 ( 2 ), were synthesized and characterized by elementa...
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| Veröffentlicht in: | New journal of chemistry 2020-07, Vol.44 (27), p.11471-11489 |
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| creator | Ramesh, Golla Pillegowda, Manohar Periyasamy, Ganga Suchetan, P. A Butcher, R. J Foro, Sabine Nagaraju, G |
| description | Two new ligands, 4′-(2,3,4-trimethoxyphenyl)-2,2′:6′,2′′-terpyridine (
L
1
) and 4′(2,4,5-trimethoxyphenyl)-2,2′:6′,2′′-terpyridine (
L
2
), and their homoleptic ruthenium(
ii
) complexes, [Ru(
L
1
)
2
](PF
6
)
2
(
1
) and [Ru(
L
2
)
2
](PF
6
)
2
(
2
), were synthesized and characterized by elemental analysis,
1
H and
13
C{
1
H} NMR spectroscopy, FT-IR spectroscopy and single crystal X-ray diffraction. The crystals of these compounds contain CH F, OH F, CH O, CH π and/or π π intermolecular secondary interactions, resulting in supramolecular architectures. Hirshfeld surface analysis of all four compounds was also carried out to determine the intermolecular interactions. We investigated the photophysical properties of
L
1
,
L
2
,
1
and
2
by UV-Visible absorption and fluorescence emission spectroscopy and studied their electrochemical properties by cyclic voltammetry. In addition to n-π* and π-π* bands in the UV-Visible spectra of both ligands and complexes, a fairly strong and relatively broad
1
MLCT band appeared at
λ
max
∼ 500 nm in complexes
1
and
2
. The emission bands in ligands
L
1
and
L
2
appeared at
λ
em
429 and 426 nm, respectively, whereas in the complexes
1
and
2
, these bands showed red-shifts of 34 and 82 nm, respectively. Both
L
1
and
L
2
showed two oxidation peaks; however, only
L
2
showed a significant reduction peak. Complexes
1
and
2
showed two oxidation peaks and two reduction peaks. The effects of increasing scan rate (100 to 1000 mV s
−1
) on the electrochemical behaviour of complexes
1
and
2
were also investigated. The experimentally observed structural and photophysical properties were supported by DFT and TD-DFT calculations.
[Ru(
L
1
)
2
](PF
6
)
2
(
1
) and [Ru(
L
2
)
2
](PF
6
)
2
(
2
): X-ray structures, CH F/O, OH F/N, CH O/π, π π interactions, absorption and emission spectra, DFT/TD-DFT, Hirshfeld analysis. |
| doi_str_mv | 10.1039/d0nj00046a |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_rsc_p</sourceid><recordid>TN_cdi_proquest_journals_2423064591</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2423064591</sourcerecordid><originalsourceid>FETCH-LOGICAL-c307t-80f89c560b64d12f9d1052740b9a6b0fd779b32351606ba0305363d07e0aa27c3</originalsourceid><addsrcrecordid>eNp9kc1u1DAUhSMEEqWwYY9kxAbQBK7jxGnYVR1KQRUsGNaRYzuNK8d2_aM2O56JR-I9kHBmEOyQLPv6nE_Xuj5F8RTDGwykeyvAXANATdm94ggT2pVdRfH9XOO6LqGp6cPiUQiZwbil-Kj49XUxcZJBhQ3ifgmRaRSiTzwmL7PmJhutm5agONMbJLXk0Vs-yXkVMpqEWrnt-Q4xI9BuW65l9njSLCprwl6_UD5Mo9Qi35jO7QKyIzLyFlWb6uf3H-9o3vZVXmWU3i1eCWUk0uoqNwjoVsUJOWkEMxHVK_UyejXLONm7xU3SLPoVuvI2ucOLeSrl0WRnq6WLiiOfsmRUmhG3s9PyTobHxYOR6SCf_DmPi2_n73dnF-Xllw8fz04vS06gjeUJjCcdbygMtBa4GjuBoanaGoaO0QFG0bbdQCrSYAp0YECgIZQIaCUwVrWcHBcvDn2dtzdJhthf2-TzR4S-qisCtG46nKnXB4p7G4KXY-_ygMwvPYZ-jbffwudP-3hPM_zsAPvA_3L_4s_-8__5vRMj-Q2qfbb1</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2423064591</pqid></control><display><type>article</type><title>Synthesis, crystal structures, photophysical, electrochemical studies, DFT and TD-DFT calculations and Hirshfeld analysis of new 2,2′:6′,2′′-terpyridine ligands with pendant 4′-(trimethoxyphenyl) groups and their homoleptic ruthenium complexes</title><source>Royal Society Of Chemistry Journals</source><source>Alma/SFX Local Collection</source><creator>Ramesh, Golla ; Pillegowda, Manohar ; Periyasamy, Ganga ; Suchetan, P. A ; Butcher, R. J ; Foro, Sabine ; Nagaraju, G</creator><creatorcontrib>Ramesh, Golla ; Pillegowda, Manohar ; Periyasamy, Ganga ; Suchetan, P. A ; Butcher, R. J ; Foro, Sabine ; Nagaraju, G</creatorcontrib><description>Two new ligands, 4′-(2,3,4-trimethoxyphenyl)-2,2′:6′,2′′-terpyridine (
L
1
) and 4′(2,4,5-trimethoxyphenyl)-2,2′:6′,2′′-terpyridine (
L
2
), and their homoleptic ruthenium(
ii
) complexes, [Ru(
L
1
)
2
](PF
6
)
2
(
1
) and [Ru(
L
2
)
2
](PF
6
)
2
(
2
), were synthesized and characterized by elemental analysis,
1
H and
13
C{
1
H} NMR spectroscopy, FT-IR spectroscopy and single crystal X-ray diffraction. The crystals of these compounds contain CH F, OH F, CH O, CH π and/or π π intermolecular secondary interactions, resulting in supramolecular architectures. Hirshfeld surface analysis of all four compounds was also carried out to determine the intermolecular interactions. We investigated the photophysical properties of
L
1
,
L
2
,
1
and
2
by UV-Visible absorption and fluorescence emission spectroscopy and studied their electrochemical properties by cyclic voltammetry. In addition to n-π* and π-π* bands in the UV-Visible spectra of both ligands and complexes, a fairly strong and relatively broad
1
MLCT band appeared at
λ
max
∼ 500 nm in complexes
1
and
2
. The emission bands in ligands
L
1
and
L
2
appeared at
λ
em
429 and 426 nm, respectively, whereas in the complexes
1
and
2
, these bands showed red-shifts of 34 and 82 nm, respectively. Both
L
1
and
L
2
showed two oxidation peaks; however, only
L
2
showed a significant reduction peak. Complexes
1
and
2
showed two oxidation peaks and two reduction peaks. The effects of increasing scan rate (100 to 1000 mV s
−1
) on the electrochemical behaviour of complexes
1
and
2
were also investigated. The experimentally observed structural and photophysical properties were supported by DFT and TD-DFT calculations.
[Ru(
L
1
)
2
](PF
6
)
2
(
1
) and [Ru(
L
2
)
2
](PF
6
)
2
(
2
): X-ray structures, CH F/O, OH F/N, CH O/π, π π interactions, absorption and emission spectra, DFT/TD-DFT, Hirshfeld analysis.</description><identifier>ISSN: 1144-0546</identifier><identifier>EISSN: 1369-9261</identifier><identifier>DOI: 10.1039/d0nj00046a</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Chemical analysis ; Coordination compounds ; Crystal structure ; Crystallography ; Electrochemical analysis ; Electrons ; Emission analysis ; Fluorescence ; Infrared spectroscopy ; Ligands ; Mathematical analysis ; NMR spectroscopy ; Oxidation ; Properties (attributes) ; Reduction ; Ruthenium compounds ; Single crystals ; Spectrum analysis ; Surface analysis (chemical)</subject><ispartof>New journal of chemistry, 2020-07, Vol.44 (27), p.11471-11489</ispartof><rights>Copyright Royal Society of Chemistry 2020</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c307t-80f89c560b64d12f9d1052740b9a6b0fd779b32351606ba0305363d07e0aa27c3</citedby><cites>FETCH-LOGICAL-c307t-80f89c560b64d12f9d1052740b9a6b0fd779b32351606ba0305363d07e0aa27c3</cites><orcidid>0000-0003-2770-7076 ; 0000-0002-8675-5935 ; 0000-0001-6522-6148</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>Ramesh, Golla</creatorcontrib><creatorcontrib>Pillegowda, Manohar</creatorcontrib><creatorcontrib>Periyasamy, Ganga</creatorcontrib><creatorcontrib>Suchetan, P. A</creatorcontrib><creatorcontrib>Butcher, R. J</creatorcontrib><creatorcontrib>Foro, Sabine</creatorcontrib><creatorcontrib>Nagaraju, G</creatorcontrib><title>Synthesis, crystal structures, photophysical, electrochemical studies, DFT and TD-DFT calculations and Hirshfeld analysis of new 2,2′:6′,2′′-terpyridine ligands with pendant 4′-(trimethoxyphenyl) groups and their homoleptic ruthenium complexes</title><title>New journal of chemistry</title><description>Two new ligands, 4′-(2,3,4-trimethoxyphenyl)-2,2′:6′,2′′-terpyridine (
L
1
) and 4′(2,4,5-trimethoxyphenyl)-2,2′:6′,2′′-terpyridine (
L
2
), and their homoleptic ruthenium(
ii
) complexes, [Ru(
L
1
)
2
](PF
6
)
2
(
1
) and [Ru(
L
2
)
2
](PF
6
)
2
(
2
), were synthesized and characterized by elemental analysis,
1
H and
13
C{
1
H} NMR spectroscopy, FT-IR spectroscopy and single crystal X-ray diffraction. The crystals of these compounds contain CH F, OH F, CH O, CH π and/or π π intermolecular secondary interactions, resulting in supramolecular architectures. Hirshfeld surface analysis of all four compounds was also carried out to determine the intermolecular interactions. We investigated the photophysical properties of
L
1
,
L
2
,
1
and
2
by UV-Visible absorption and fluorescence emission spectroscopy and studied their electrochemical properties by cyclic voltammetry. In addition to n-π* and π-π* bands in the UV-Visible spectra of both ligands and complexes, a fairly strong and relatively broad
1
MLCT band appeared at
λ
max
∼ 500 nm in complexes
1
and
2
. The emission bands in ligands
L
1
and
L
2
appeared at
λ
em
429 and 426 nm, respectively, whereas in the complexes
1
and
2
, these bands showed red-shifts of 34 and 82 nm, respectively. Both
L
1
and
L
2
showed two oxidation peaks; however, only
L
2
showed a significant reduction peak. Complexes
1
and
2
showed two oxidation peaks and two reduction peaks. The effects of increasing scan rate (100 to 1000 mV s
−1
) on the electrochemical behaviour of complexes
1
and
2
were also investigated. The experimentally observed structural and photophysical properties were supported by DFT and TD-DFT calculations.
[Ru(
L
1
)
2
](PF
6
)
2
(
1
) and [Ru(
L
2
)
2
](PF
6
)
2
(
2
): X-ray structures, CH F/O, OH F/N, CH O/π, π π interactions, absorption and emission spectra, DFT/TD-DFT, Hirshfeld analysis.</description><subject>Chemical analysis</subject><subject>Coordination compounds</subject><subject>Crystal structure</subject><subject>Crystallography</subject><subject>Electrochemical analysis</subject><subject>Electrons</subject><subject>Emission analysis</subject><subject>Fluorescence</subject><subject>Infrared spectroscopy</subject><subject>Ligands</subject><subject>Mathematical analysis</subject><subject>NMR spectroscopy</subject><subject>Oxidation</subject><subject>Properties (attributes)</subject><subject>Reduction</subject><subject>Ruthenium compounds</subject><subject>Single crystals</subject><subject>Spectrum analysis</subject><subject>Surface analysis (chemical)</subject><issn>1144-0546</issn><issn>1369-9261</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNp9kc1u1DAUhSMEEqWwYY9kxAbQBK7jxGnYVR1KQRUsGNaRYzuNK8d2_aM2O56JR-I9kHBmEOyQLPv6nE_Xuj5F8RTDGwykeyvAXANATdm94ggT2pVdRfH9XOO6LqGp6cPiUQiZwbil-Kj49XUxcZJBhQ3ifgmRaRSiTzwmL7PmJhutm5agONMbJLXk0Vs-yXkVMpqEWrnt-Q4xI9BuW65l9njSLCprwl6_UD5Mo9Qi35jO7QKyIzLyFlWb6uf3H-9o3vZVXmWU3i1eCWUk0uoqNwjoVsUJOWkEMxHVK_UyejXLONm7xU3SLPoVuvI2ucOLeSrl0WRnq6WLiiOfsmRUmhG3s9PyTobHxYOR6SCf_DmPi2_n73dnF-Xllw8fz04vS06gjeUJjCcdbygMtBa4GjuBoanaGoaO0QFG0bbdQCrSYAp0YECgIZQIaCUwVrWcHBcvDn2dtzdJhthf2-TzR4S-qisCtG46nKnXB4p7G4KXY-_ygMwvPYZ-jbffwudP-3hPM_zsAPvA_3L_4s_-8__5vRMj-Q2qfbb1</recordid><startdate>20200721</startdate><enddate>20200721</enddate><creator>Ramesh, Golla</creator><creator>Pillegowda, Manohar</creator><creator>Periyasamy, Ganga</creator><creator>Suchetan, P. A</creator><creator>Butcher, R. J</creator><creator>Foro, Sabine</creator><creator>Nagaraju, G</creator><general>Royal Society of Chemistry</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>H9R</scope><scope>JG9</scope><scope>KA0</scope><orcidid>https://orcid.org/0000-0003-2770-7076</orcidid><orcidid>https://orcid.org/0000-0002-8675-5935</orcidid><orcidid>https://orcid.org/0000-0001-6522-6148</orcidid></search><sort><creationdate>20200721</creationdate><title>Synthesis, crystal structures, photophysical, electrochemical studies, DFT and TD-DFT calculations and Hirshfeld analysis of new 2,2′:6′,2′′-terpyridine ligands with pendant 4′-(trimethoxyphenyl) groups and their homoleptic ruthenium complexes</title><author>Ramesh, Golla ; Pillegowda, Manohar ; Periyasamy, Ganga ; Suchetan, P. A ; Butcher, R. J ; Foro, Sabine ; Nagaraju, G</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c307t-80f89c560b64d12f9d1052740b9a6b0fd779b32351606ba0305363d07e0aa27c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Chemical analysis</topic><topic>Coordination compounds</topic><topic>Crystal structure</topic><topic>Crystallography</topic><topic>Electrochemical analysis</topic><topic>Electrons</topic><topic>Emission analysis</topic><topic>Fluorescence</topic><topic>Infrared spectroscopy</topic><topic>Ligands</topic><topic>Mathematical analysis</topic><topic>NMR spectroscopy</topic><topic>Oxidation</topic><topic>Properties (attributes)</topic><topic>Reduction</topic><topic>Ruthenium compounds</topic><topic>Single crystals</topic><topic>Spectrum analysis</topic><topic>Surface analysis (chemical)</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ramesh, Golla</creatorcontrib><creatorcontrib>Pillegowda, Manohar</creatorcontrib><creatorcontrib>Periyasamy, Ganga</creatorcontrib><creatorcontrib>Suchetan, P. A</creatorcontrib><creatorcontrib>Butcher, R. J</creatorcontrib><creatorcontrib>Foro, Sabine</creatorcontrib><creatorcontrib>Nagaraju, G</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Illustrata: Natural Sciences</collection><collection>Materials Research Database</collection><collection>ProQuest Illustrata: Technology Collection</collection><jtitle>New journal of chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ramesh, Golla</au><au>Pillegowda, Manohar</au><au>Periyasamy, Ganga</au><au>Suchetan, P. A</au><au>Butcher, R. J</au><au>Foro, Sabine</au><au>Nagaraju, G</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis, crystal structures, photophysical, electrochemical studies, DFT and TD-DFT calculations and Hirshfeld analysis of new 2,2′:6′,2′′-terpyridine ligands with pendant 4′-(trimethoxyphenyl) groups and their homoleptic ruthenium complexes</atitle><jtitle>New journal of chemistry</jtitle><date>2020-07-21</date><risdate>2020</risdate><volume>44</volume><issue>27</issue><spage>11471</spage><epage>11489</epage><pages>11471-11489</pages><issn>1144-0546</issn><eissn>1369-9261</eissn><abstract>Two new ligands, 4′-(2,3,4-trimethoxyphenyl)-2,2′:6′,2′′-terpyridine (
L
1
) and 4′(2,4,5-trimethoxyphenyl)-2,2′:6′,2′′-terpyridine (
L
2
), and their homoleptic ruthenium(
ii
) complexes, [Ru(
L
1
)
2
](PF
6
)
2
(
1
) and [Ru(
L
2
)
2
](PF
6
)
2
(
2
), were synthesized and characterized by elemental analysis,
1
H and
13
C{
1
H} NMR spectroscopy, FT-IR spectroscopy and single crystal X-ray diffraction. The crystals of these compounds contain CH F, OH F, CH O, CH π and/or π π intermolecular secondary interactions, resulting in supramolecular architectures. Hirshfeld surface analysis of all four compounds was also carried out to determine the intermolecular interactions. We investigated the photophysical properties of
L
1
,
L
2
,
1
and
2
by UV-Visible absorption and fluorescence emission spectroscopy and studied their electrochemical properties by cyclic voltammetry. In addition to n-π* and π-π* bands in the UV-Visible spectra of both ligands and complexes, a fairly strong and relatively broad
1
MLCT band appeared at
λ
max
∼ 500 nm in complexes
1
and
2
. The emission bands in ligands
L
1
and
L
2
appeared at
λ
em
429 and 426 nm, respectively, whereas in the complexes
1
and
2
, these bands showed red-shifts of 34 and 82 nm, respectively. Both
L
1
and
L
2
showed two oxidation peaks; however, only
L
2
showed a significant reduction peak. Complexes
1
and
2
showed two oxidation peaks and two reduction peaks. The effects of increasing scan rate (100 to 1000 mV s
−1
) on the electrochemical behaviour of complexes
1
and
2
were also investigated. The experimentally observed structural and photophysical properties were supported by DFT and TD-DFT calculations.
[Ru(
L
1
)
2
](PF
6
)
2
(
1
) and [Ru(
L
2
)
2
](PF
6
)
2
(
2
): X-ray structures, CH F/O, OH F/N, CH O/π, π π interactions, absorption and emission spectra, DFT/TD-DFT, Hirshfeld analysis.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d0nj00046a</doi><tpages>19</tpages><orcidid>https://orcid.org/0000-0003-2770-7076</orcidid><orcidid>https://orcid.org/0000-0002-8675-5935</orcidid><orcidid>https://orcid.org/0000-0001-6522-6148</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1144-0546 |
| ispartof | New journal of chemistry, 2020-07, Vol.44 (27), p.11471-11489 |
| issn | 1144-0546 1369-9261 |
| language | eng |
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| source | Royal Society Of Chemistry Journals; Alma/SFX Local Collection |
| subjects | Chemical analysis Coordination compounds Crystal structure Crystallography Electrochemical analysis Electrons Emission analysis Fluorescence Infrared spectroscopy Ligands Mathematical analysis NMR spectroscopy Oxidation Properties (attributes) Reduction Ruthenium compounds Single crystals Spectrum analysis Surface analysis (chemical) |
| title | Synthesis, crystal structures, photophysical, electrochemical studies, DFT and TD-DFT calculations and Hirshfeld analysis of new 2,2′:6′,2′′-terpyridine ligands with pendant 4′-(trimethoxyphenyl) groups and their homoleptic ruthenium complexes |
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