Syntheses, Spectroscopic, Electrochemical, and Third-Order Nonlinear Optical Studies of a Hybrid Tris{ruthenium(alkynyl)/(2-phenylpyridine)}iridium Complex
The synthesis of fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C C-1-C6H2-3,5-Et2-4-C CC6H4-4-C CH)}3] (10), which bears pendant ethynyl groups, and its reaction with [RuCl(dppe)2]PF6 to afford the heterobimetallic complex fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C C-1-C6H2-3,5-Et2-4-C CC6H4-4-C C-trans-[RuCl(dppe)2])}3...
| Main Authors: | , , , , , , , , , |
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| Format: | Journal Article |
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2015
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| Online Access: | http://hdl.handle.net/20.500.11937/33156 |
| _version_ | 1848753867038130176 |
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| author | Zhao, H. Simpson, Peter Barlow, A. Moxey, G. Morshedi, M. Roy, N. Philip, R. Zhang, C. Cifuentes, M. Humphrey, M. |
| author_facet | Zhao, H. Simpson, Peter Barlow, A. Moxey, G. Morshedi, M. Roy, N. Philip, R. Zhang, C. Cifuentes, M. Humphrey, M. |
| author_sort | Zhao, H. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | The synthesis of fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C C-1-C6H2-3,5-Et2-4-C CC6H4-4-C CH)}3] (10), which bears pendant ethynyl groups, and its reaction with [RuCl(dppe)2]PF6 to afford the heterobimetallic complex fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C C-1-C6H2-3,5-Et2-4-C CC6H4-4-C C-trans-[RuCl(dppe)2])}3] (11) is described. Complex 10 is available from the two-step formation of iodo-functionalized fac-tris[2-(4-iodophenyl)pyridine]iridium(III) (6), followed by ligand-centered palladium-catalyzed coupling and desilylation reactions. Structural studies of tetrakis[2-(4-iodophenyl)pyridine-N,C1′](μ-dichloro)diiridium 5, 6, fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C C-1-C6H2-3,5-Et2-4-C CH)}3] (8), and 10 confirm ligand-centered derivatization of the tris(2-phenylpyridine)iridium unit.Electrochemical studies reveal two (5) or one (6–10) Ir-centered oxidations for which the potential is sensitive to functionalization at the phenylpyridine groups but relatively insensitive to more remote derivatization. Compound 11 undergoes sequential Ru-centered and Ir-centered oxidation, with the potential of the latter significantly more positive than that of Ir(N,C′-NC5H4-2-C6H4-2)3. Ligand-centered π–π* transitions characteristic of the Ir(N,C′-NC5H4-2-C6H4-2)3 unit red-shift and gain in intensity following the iodo and alkynyl incorporation. Spectroelectrochemical studies of 6, 7, 9, and 11 reveal the appearance in each case of new low-energy LMCT bands following formal IrIII/IV oxidation preceded, in the case of 11, by the appearance of a low-energy LMCT band associated with the formal RuII/III oxidation process. Emission maxima of 6–10 reveal a red-shift upon alkynyl group introduction and arylalkynyl π-system lengthening; this process is quenched upon incorporation of the ligated ruthenium moiety on proceeding to 11. Third-order nonlinear optical studies of 11 were undertaken at the benchmark wavelengths of 800 nm (fs pulses) and 532 nm (ns pulses), the results from the former suggesting a dominant contribution from two-photon absorption, and results from the latter being consistent with primarily excited-state absorption. |
| first_indexed | 2025-11-14T08:31:20Z |
| format | Journal Article |
| id | curtin-20.500.11937-33156 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T08:31:20Z |
| publishDate | 2015 |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-331562017-09-13T15:29:12Z Syntheses, Spectroscopic, Electrochemical, and Third-Order Nonlinear Optical Studies of a Hybrid Tris{ruthenium(alkynyl)/(2-phenylpyridine)}iridium Complex Zhao, H. Simpson, Peter Barlow, A. Moxey, G. Morshedi, M. Roy, N. Philip, R. Zhang, C. Cifuentes, M. Humphrey, M. The synthesis of fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C C-1-C6H2-3,5-Et2-4-C CC6H4-4-C CH)}3] (10), which bears pendant ethynyl groups, and its reaction with [RuCl(dppe)2]PF6 to afford the heterobimetallic complex fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C C-1-C6H2-3,5-Et2-4-C CC6H4-4-C C-trans-[RuCl(dppe)2])}3] (11) is described. Complex 10 is available from the two-step formation of iodo-functionalized fac-tris[2-(4-iodophenyl)pyridine]iridium(III) (6), followed by ligand-centered palladium-catalyzed coupling and desilylation reactions. Structural studies of tetrakis[2-(4-iodophenyl)pyridine-N,C1′](μ-dichloro)diiridium 5, 6, fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C C-1-C6H2-3,5-Et2-4-C CH)}3] (8), and 10 confirm ligand-centered derivatization of the tris(2-phenylpyridine)iridium unit.Electrochemical studies reveal two (5) or one (6–10) Ir-centered oxidations for which the potential is sensitive to functionalization at the phenylpyridine groups but relatively insensitive to more remote derivatization. Compound 11 undergoes sequential Ru-centered and Ir-centered oxidation, with the potential of the latter significantly more positive than that of Ir(N,C′-NC5H4-2-C6H4-2)3. Ligand-centered π–π* transitions characteristic of the Ir(N,C′-NC5H4-2-C6H4-2)3 unit red-shift and gain in intensity following the iodo and alkynyl incorporation. Spectroelectrochemical studies of 6, 7, 9, and 11 reveal the appearance in each case of new low-energy LMCT bands following formal IrIII/IV oxidation preceded, in the case of 11, by the appearance of a low-energy LMCT band associated with the formal RuII/III oxidation process. Emission maxima of 6–10 reveal a red-shift upon alkynyl group introduction and arylalkynyl π-system lengthening; this process is quenched upon incorporation of the ligated ruthenium moiety on proceeding to 11. Third-order nonlinear optical studies of 11 were undertaken at the benchmark wavelengths of 800 nm (fs pulses) and 532 nm (ns pulses), the results from the former suggesting a dominant contribution from two-photon absorption, and results from the latter being consistent with primarily excited-state absorption. 2015 Journal Article http://hdl.handle.net/20.500.11937/33156 10.1002/chem.201500951 restricted |
| spellingShingle | Zhao, H. Simpson, Peter Barlow, A. Moxey, G. Morshedi, M. Roy, N. Philip, R. Zhang, C. Cifuentes, M. Humphrey, M. Syntheses, Spectroscopic, Electrochemical, and Third-Order Nonlinear Optical Studies of a Hybrid Tris{ruthenium(alkynyl)/(2-phenylpyridine)}iridium Complex |
| title | Syntheses, Spectroscopic, Electrochemical, and Third-Order Nonlinear Optical Studies of a Hybrid Tris{ruthenium(alkynyl)/(2-phenylpyridine)}iridium Complex |
| title_full | Syntheses, Spectroscopic, Electrochemical, and Third-Order Nonlinear Optical Studies of a Hybrid Tris{ruthenium(alkynyl)/(2-phenylpyridine)}iridium Complex |
| title_fullStr | Syntheses, Spectroscopic, Electrochemical, and Third-Order Nonlinear Optical Studies of a Hybrid Tris{ruthenium(alkynyl)/(2-phenylpyridine)}iridium Complex |
| title_full_unstemmed | Syntheses, Spectroscopic, Electrochemical, and Third-Order Nonlinear Optical Studies of a Hybrid Tris{ruthenium(alkynyl)/(2-phenylpyridine)}iridium Complex |
| title_short | Syntheses, Spectroscopic, Electrochemical, and Third-Order Nonlinear Optical Studies of a Hybrid Tris{ruthenium(alkynyl)/(2-phenylpyridine)}iridium Complex |
| title_sort | syntheses, spectroscopic, electrochemical, and third-order nonlinear optical studies of a hybrid tris{ruthenium(alkynyl)/(2-phenylpyridine)}iridium complex |
| url | http://hdl.handle.net/20.500.11937/33156 |