Skip to main content
SpringerLink
Log in

Theoretical study on second-order nonlinear optical properties of 1,10-phenanthroline Ru(II) complexes

  • Articles
  • Published:
Science China Chemistry Aims and scope Submit manuscript

Abstract

The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru(II) complexes were carried out using density functional theory (DFT). The results indicate that these complexes have large second-order nonlinear optical (NLO) responses. Specially, complex 6b has a maximal first hyperpolarizability βtot value. The first hyperpolarizabilities can be tuned by changing the ancillary ligand, introducing electron-acceptor group NO2 and/or increasing π-conjugation on phenanthroline. Calculations on absorption spectra demonstrate that the second-order NLO responses of complexes in series a are ascribed to the intraligand charge transfer (ILCT), while the complexes in series b exhibit metal-to-ligand charge transfer (MLCT) and ligand-to-ligand charge transfer (LLCT) transition at relatively low-energy absorptions.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Zyss J. Molecular Nonlinear Optics: Materials, Physics, and Devices. Boston: Academic Press, 1994

    Google Scholar 

  2. Allis DG, Spencer JT. Polyhedral-based nonlinear optical materials. 2.1 Theoretical investigation of some new high nonlinear optical response compounds involving polyhedral bridges with charged aromatic donors and acceptors. Inorg Chem, 2001, 40: 3373–3380

    Article  CAS  Google Scholar 

  3. Coe BJ, Harris JA, Jones LA, Brunschwig BS, Song K, Clays K, Garin J, Orduna J, Coles SJ, Hursthouse MB. Syntheses and properties of two-dimensional charged nonlinear optical chromophores incorporating redox-switchable cis-tetraammineruthenium(II) centers. J Am Chem Soc, 2005, 127: 4845–4859

    Article  CAS  Google Scholar 

  4. Liu XD, Qiu YQ, Chen H, Li N, Sun SL, Su ZM. DFT study on second-order nonlinear optical properties of Pt(II) complexes with different chromophores. Sci China Ser B: Chem, 2009, 52: 144–152

    Article  CAS  Google Scholar 

  5. Roberto D, Ugo R, Tessore F, Lucenti E, Quici S, Vezza S, Fantucci PC, Invernizzi I, Bruni S, Lendoux-Rak I, Zyss J. Effect of the coordination to M(II) metal centers (M = Zn, Cd, Pt) on the quadratic hyperpolarizability of various substituted 5-X-1,10-phenanthrolines (X = donor group) and of trans-4-(dimethylamino)-4′-stilbazole. Organometallics, 2002, 21: 161–170

    Article  CAS  Google Scholar 

  6. Pizzotti M, Ugo R, Dragonetti C, Annoni E. Unexpected formation of a weak metal-metal bond: Synthesis, electronic properties, and second-order NLO responses of push-pull late-early heteronuclear bimetallic complexes with W(CO)3(1,10-phenanthroline) acting as a donor ligand. Organometallics, 2003, 22: 4001–4011

    Article  CAS  Google Scholar 

  7. Das S, Jana A, Ramanathan V, Chakraborty T, Ghosh S, Das PK, Bharadwaj PK. Design and synthesis of 1,10-phenanthroline based Zn(II) complexes bearing 1D push-pull NLO-phores for tunable quadratic nonlinear optical properties. J Organomet Chem, 2006, 691: 2512–25

    Article  CAS  Google Scholar 

  8. Dragonetti C, Righetto S, Roberto D, Ugo R, Valore A, Fantacci S, Sgamellotti A, Angelis FDe. Cyclometallated iridium(III) complexes with substituted 1,10-phenanthrolines: A new class of highly active organometallic second order NLO-phores with excellent transparency with respect to second harmonic emission. Chem Commun, 2007, 4116–4118

  9. Dragonetti C, Righetto S, Roberto D, Ugo R, Valore A, Demartin F, Angelies FDe, Antonio S, Fantacci S. The role of 5-R-1,10-phenan-throline (R = CH3, NO2) on the emission properties and second-order NLO response of cationic Ir(III) organometallic chromophores. Inorganica Chimica Acta, 2008, 361: 4070–4076

    Article  CAS  Google Scholar 

  10. Valore A, Cariati E, Dragonetti C, Righetto S, Ugo R, Angelis FDe, Fantacci S, Sgamellotti A, Macchioni A, Zuccaccia D. Cyclometalated Ir(III) complexes with substituted 1,10-Phenanthrolines: A new class of efficient cationic organometallic second-order NLO chromophores. Chem Eur J, 2010, 16: 4814–4825

    Article  CAS  Google Scholar 

  11. Chakravarty J, Bhattacharya S. Synthesis, characterization, electron-transfer properties and reactivities of a group of ruthenium(II) complexes with RuN2P2X2 (X = Cl, Br) coordination spheres. Polyhedron, 1994, 13: 2671–2678

    Article  CAS  Google Scholar 

  12. Aguirre P, Sariego R, Moya SA. Ruthenium(II) complexes in catalytic oxidation. J Coord Chem, 2001, 54: 401–413

    Article  CAS  Google Scholar 

  13. Valore A, Balordi M, Colombo A, Dragonetti C, Righetto S, Roberto D, Ugo R, Benincori T, Rampinini G, Sannicolò F, Demartin F. Novel ruthenium(II) complexes with substituted 1,10-phenanthroline or 4,5-diazafluorene linked to a fullerene as highly active second order NLO chromophores. Dalton Trans, 2010, 39: 10314–10318

    Article  CAS  Google Scholar 

  14. Karna SP, Dupuis M. Frequency dependent nonlinear optical properties of molecules: Formulation and implementation in the HONDO program. J Comput Chem, 1991, 12: 487–504

    Article  CAS  Google Scholar 

  15. Sim F, Chin S, Dupuis M, Rice JE. Electron correlation effects in hyperpolarizabilities of p-nitroaniline. J Phys Chem, 1993, 97: 1158–1163

    Article  CAS  Google Scholar 

  16. Frisch M, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Nor mand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ. Gaussian 09, Revision A.1, Wallingford CT: Gaussian, Inc, 2009

    Google Scholar 

  17. Dolg M, Stoll H, Preuss H. A combination of quasirelativistic pseudopotential and ligand field calculations for lanthanoid compounds. Theor Chim Acta, 1993, 85: 441–450

    Article  CAS  Google Scholar 

  18. Andrae D, Haußermann U, Dolg M, Preuß H. Energy-adjustedab initio pseudopotentials for the second and third row transition elements. Theo Chim Acta, 1990, 77: 123–141

    Article  CAS  Google Scholar 

  19. Oudar JL. Optical nonlinearities of conjugated molecules. Stilbene derivatives and highly polar aromatic compounds. J Chem Phys, 1977, 67: 446–457

    CAS  Google Scholar 

  20. Oudar JL, Chemla DS, Hyperpolarizabilities of the nitroanilines and their relations to the excited state dipole moment. J Chem Phys, 1976, 66: 2664–2668

    Article  Google Scholar 

  21. Karton A, Iron MA, van der Boom ME, Martin JML. NLO properties of metallabenzene-based chromophores: A time-dependent density functional study. J Phys Chem A, 2005, 109, 5454-5462

  22. Coe BJ, Harries JL, Helliwell M, Jones LA, Asselberghs I, Clays K, Brunschwig BS, Harris JA, Garín J, Orduna J. Pentacyanoiron(II) as an electron donor group for nonlinear optics: Medium-responsive properties and comparisons with related pentaannineruthenium(II) complexes. J Am Chem Soc, 2006, 128: 12192–12204

    Article  CAS  Google Scholar 

  23. Janjua MRSA, Guan W, Yan LK, Su ZM, Karim A, Akbar J. Quantum chemical design for enhanced second-order NLO response of terpyridine-substituted hexamolybdates. Eur J Inorg Chem, 2010, 3466–3472

Download references

Author information

Authors and Affiliations

  1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, China

    CunHuan Wang, NaNa Ma, ShiLing Sun & YongQing Qiu

Authors
  1. CunHuan Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. NaNa Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. ShiLing Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. YongQing Qiu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to YongQing Qiu.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Wang, C., Ma, N., Sun, S. et al. Theoretical study on second-order nonlinear optical properties of 1,10-phenanthroline Ru(II) complexes. Sci. China Chem. 55, 1421–1427 (2012). https://doi.org/10.1007/s11426-012-4668-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11426-012-4668-9

Keywords

Search

Navigation