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  Combined Experimental and Theoretical Investigation of Ligand and Anion Controlled Complex Formation with Unprecedented Structural Features and Photoluminescence Properties of Zinc(II) Complexes

Chakraborty, P., Adhikary, J., Samanta, S., Escudero, D., Castro, A. C., Swart, M., et al. (2014). Combined Experimental and Theoretical Investigation of Ligand and Anion Controlled Complex Formation with Unprecedented Structural Features and Photoluminescence Properties of Zinc(II) Complexes. Crystal Growth & Design, 14(8), 4111-4123. doi:10.1021/cg500717n.

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Chakraborty, Prateeti1, Author
Adhikary, Jaydeep1, Author
Samanta, Sugata2, Author
Escudero, Daniel3, Author              
Castro, Abril C.4, Author
Swart, Marcel4, 5, Author
Ghosh, Sanjib2, Author
Bauzá, Antonio6, Author
Frontera, Antonio6, Author
Zangrando, Ennio7, Author
Das, Debasis1, Author
Affiliations:
1Department of Chemistry, University of Calcutta, A. P. C. Road, Kolkata 700009, India, ou_persistent22              
2Department of Chemistry, Presidency University, Kolkata 700073, India, ou_persistent22              
3Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              
4Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus de Montilivi, 17071 Girona, Catalonia, Spain, ou_persistent22              
5Institució Catalana de Recerca i Estudis Avançats (ICREA), Pg. Lluís Companys 23, 08010 Barcelona, Catalonia, Spain, ou_persistent22              
6Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma, Baleares, Spain, ou_persistent22              
7Department of Chemical and Pharmaceutical Sciences, University of Trieste, ou_persistent22              

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 Abstract: By using two potential tridentate ligands, HL1 [4-chloro-2-[(2-morpholin-4-yl-ethylimino)-methyl]-phenol] and HL2 [4-chloro-2-[(3-morpholin-4-yl-propylimino)-methyl]-phenol], which differ by one methylene group in the alkyl chain, four new ZnII complexes, namely, [Zn(L2H)2](ClO4)2 (1), [Zn(L1)(H2O)2][Zn(L1)(SCN)2] (2), [Zn(L1)(dca)]n (3), and [Zn2(L1)2(N3)2(H2O)2] (4) [where dca = dicyanamide anion] were synthesized and structurally characterized. The results indicate that the slight structural difference between the ligands, HL1 and HL2, because of the one methylene group connecting the nitrogen atoms provokes a chemical behavior completely different from what was expected. Any attempt to isolate the Zn(L2) complexes with thiocyanato, dicyanamido, and azide was unsuccessful, and perchlorate complex 1 was always obtained. In contrast, with HL1 we obtained structural diversity on varying the anions, but we failed to isolate the analogous perchlorate complex of HL1. Single-crystal X-ray analyses revealed that the morpholine nitrogen of ligand L2 is protonated and thus does not take part in coordination with ZnII in complex 1. On the other hand, the morpholine nitrogen of L1 is coordinated to ZnII in 2–4. Of these, 2 and 4 are rare examples of a cocrystallized cationic/anionic complex and of a dinuclear complex bridged by a single azide, respectively. Some of these unexpected findings and some interesting noncovalent interactions leading to the formation of dimeric entities in solid-state compound 4 were rationalized by a DFT approach. Photoluminescence properties of the complexes as well as the ligands were investigated in solution at ambient temperature and at 77 K. The very fast photoinduced electron transfer (PET) from the nitrogen lone pair to the conjugated phenolic moiety is responsible for very low quantum yield (Φ) exhibited by the ligands, whereas complexation prevents PET, thus enhancing the Φ in the complexes. The origin of the electronic and photoluminescence properties of the ligands and complexes was assessed in light of theoretical calculations.

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Language(s): eng - English
 Dates: 2014-06-172014-05-162014-06-242014-08-06
 Publication Status: Published in print
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 Rev. Type: Peer
 Identifiers: DOI: 10.1021/cg500717n
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Title: Crystal Growth & Design
  Other : Cryst. Growth Des.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 14 (8) Sequence Number: - Start / End Page: 4111 - 4123 Identifier: ISSN: 1528-7483
CoNE: https://pure.mpg.de/cone/journals/resource/110978984570353