Synthesis, Crystal Structure and Photophysical Properties of Lanthanide Coordination Polymers of 4- 4-(9H-Carbazol-9-Yl)Butoxy Benzoate: The Effect of Bidentate Nitrogen Donors on Luminescence

dc.contributor.utaustinauthorVasudevan, Kalyan V.en_US
dc.contributor.utaustinauthorCowley, Alan H.en_US
dc.creatorRaphael, Shynien_US
dc.creatorReddy, M. L. P.en_US
dc.creatorVasudevan, Kalyan V.en_US
dc.creatorCowley, Alan H.en_US
dc.description.abstractA new aromatic carboxylate ligand, 4-[4-(9H-carbazol-9-yl)butoxy]benzoic acid (HL), has been synthesized by the replacement of the hydroxyl hydrogen of 4-hydroxy benzoic acid with a 9-butyl-9H-carbazole moiety. The anion derived from HL has been used for the support of a series of lanthanide coordination compounds [Ln = Eu (1), Gd (2) and Tb (3)]. The new lanthanide complexes have been characterized by a variety of spectroscopic techniques. Complex 3 was structurally authenticated by single-crystal X-ray diffraction and found to exist as a solvent-free 1D coordination polymer with the formula [Tb(L)(3)](n). The structural data reveal that the terbium atoms in compound 3 reside in an octahedral ligand environment that is somewhat unusual for a lanthanide. It is interesting to note that each carboxylate group exhibits only a bridging-bidentate mode, with a complete lack of more complex connectivities that are commonly observed for extended lanthanide-containing solid-state structures. Examination of the packing diagram for 3 revealed the existence of two-dimensional molecular arrays held together by means of CH-pi interactions. Aromatic carboxylates of the lanthanides are known to exhibit highly efficient luminescence, thus offering the promise of applicability as optical devices. However, due to difficulties that arise on account of their polymeric nature, their practical application is somewhat limited. Accordingly, synthetic routes to discrete molecular species are highly desirable. For this purpose, a series of ternary lanthanide complexes was designed, synthesized and characterized, namely [Eu(L)(3)(phen)] (4), [Eu(L)(3)(tmphen)] (5), [Tb(L)(3)(phen)] (6) and [Tb(L)(3)(tmphen)] (7) (phen = 1,10-phenanthroline and tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline). The photophysical properties of the foregoing complexes in the solid state at room temperature have been investigated. The quantum yields of the ternary complexes 4 (9.65%), 5 (21.00%), 6 (14.07%) and 7 (32.42%), were found to be significantly enhanced in the presence of bidentate nitrogen donors when compared with those of the corresponding binary compounds 1 (0.11%) and 3 (1.45%). Presumably this is due to effective energy transfer from the ancillary ligands.en_US
dc.description.sponsorshipCouncil of Scientific and Industrial Research (CSIR-TAPSUN Project) SSL, NWP-55en_US
dc.description.sponsorshipCSIR, New Delhien_US
dc.description.sponsorshipRobert A. Welch Foundation F-0003en_US
dc.identifier.citationRaphael, Shyni, M. L. P. Reddy, Kalyan V. Vasudevan, and Alan H. Cowley. "Synthesis, crystal structure and photophysical properties of lanthanide coordination polymers of 4-[4-(9 H-carbazol-9-yl) butoxy] benzoate: the effect of bidentate nitrogen donors on luminescence." Dalton Transactions 41, no. 48 (Sep., 2012): 14671-14682.en_US
dc.relation.ispartofserialDalton Transactionsen_US
dc.rightsAdministrative deposit of works to Texas ScholarWorks: This works author(s) is or was a University faculty member, student or staff member; this article is already available through open access or the publisher allows a PDF version of the article to be freely posted online. The library makes the deposit as a matter of fair use (for scholarly, educational, and research purposes), and to preserve the work and further secure public access to the works of the University.en_US
dc.subjectearth benzoate complexesen_US
dc.subjecthigh thermal-stabilityen_US
dc.subject4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxideen_US
dc.subjecteuropium complexesen_US
dc.subjectquantum yieldsen_US
dc.subjectchemistry, inorganic & nuclearen_US
dc.titleSynthesis, Crystal Structure and Photophysical Properties of Lanthanide Coordination Polymers of 4- 4-(9H-Carbazol-9-Yl)Butoxy Benzoate: The Effect of Bidentate Nitrogen Donors on Luminescenceen_US

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