Skip to main content
SpringerLink
Log in

Metal–Organic Frameworks for Second-Order Nonlinear Optics

  • Chapter
  • First Online:
Metal-Organic Frameworks for Photonics Applications

Part of the book series: Structure and Bonding ((STRUCTURE,volume 157))

Abstract

In this chapter, we highlight recent advances and perspectives in the design and synthesis of NLO-active metal–organic frameworks (MOFs). Some of these compounds show impressive second harmonic generation (SHG) responses and may have potential use in NLO-applications. Noncentrosymmetric MOFs can be synthesized mainly by using chiral ligands, unsymmetrical achiral ligands, and mixed metal ions. Organic ligands containing donor-π-acceptor systems can be incorporated into MOFs to improve the SHG activity of the bulk materials through push–pull effect. Some diamondoid or octupolar MOFs have been shown to exhibit excellent SHG properties. Besides, a number of MOFs with 2D grid-type or 1D helical chain structures display good SHG activity.

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

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 169.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 219.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 219.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Abbreviations

1,3-bimb:

1,3-Bis(imidazol-1-ylmethyl)-benzene

1,4-bimb:

1,4-Bis(imidazol-1-ylmethyl)-benzene

4-pya:

4-Pyridylacrylate

aptz:

5-(6-Aminopyridin-3-yl)tetrazol-1-ide

BCDC:

N,N′-bis(4-cyanophenyl)-(1R,2R)-diaminocyclohexane

cda:

Carbamyldicyanomethanide anion

d-H2ca:

d-camphoric acid

DMF:

N,N-dimethylformamide

DPASD:

4-(4-(Diphenylamino)styryl)-1-dodecylpyridinium

dpys:

4,4′-Dipyridylsulfide

DSAT:

4-N,N-dimethylamino-4′-N′-methyl-stilbazolium tosylate

(E)-4-pyv-3-bza:

(E)-3-(2-(4-Pyridyl)vinyl)benzoate

(E)-4-pyv-4-bza:

(E)-4-(2-(4-pyridyl)vinyl)benzoate

H2dnty:

3,5-Dinitrotyrosine

H2nicO:

6-Hydroxynicotinic acid

H2oba:

4,4′-Oxybis(benzoic acid)

H2SCMC:

S-carboxymethyl-l-cysteine

H2sdba:

4,4′-Sulfonyldibenzoic acid

H3tzpbin:

(1R,2R)-1-(3-(1H-tetrazol-5-yl)phenyl)-2-(pyridin-4-yl)-2,3-dihydro-1H-benzo[e]indole

HAmidn:

2-Amino-4,5-imidazoledicarbonitrile

H-Imazethapyr:

(2-(4,5-Dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-5-ethyl-3-pyridinecarboxylic acid

Htrtr:

3-(1,2,4-Triazole-4-yl)-1H-1,2,4-triazole

Htzpbin:

1-(3-(1H-tetrazol-5-yl)phenyl)-2-(pyridin-4-yl)-3H-benzo[e]indole

inic:

Isonicotinate

m-H2bdc:

1,3-Benzenedicarboxylic acid

nic:

Nicotinate

OH-m-H2bdc:

5-Hydroxyisophthalic acid

phen:

1,10-Phenanthroline

pyb:

4-(4-Pyridyl)benzoate

quin-6-c:

Quinoline-6-carboxylate

spcp:

4-Sulfanylmethyl-4′-phenylcarboxylate pyridine

THF:

Tetrahydrofuran

References

  1. Franken PA, Hill AE, Peters CW, Weinreich G (1961) Generation of optical harmonics. Phys Rev Lett 7:118–119

    Article  Google Scholar 

  2. Saleh BEA, Teich MC (1991) Fundamentals of photonics. Wiley, New York

    Book  Google Scholar 

  3. Boyd RW (1992) Nonlinear optics. Academic, San Diego

    Google Scholar 

  4. Zyss J (1994) Molecular nonlinear optics, materials, physics and devices. Academic, New York

    Google Scholar 

  5. Fan YX, Eckardt RC, Byer RL, Route RK, Feigelson RS (1984) AgGaS2 infrared parametric oscillator. Appl Phys Lett 45:313–315

    Article  CAS  Google Scholar 

  6. Glass AM (1988) Materials for photonic switching and Information processing. MRS Bull 13:16–20

    CAS  Google Scholar 

  7. Donaldson WR, Tang CL (1984) Urea optical parametric oscillator. Appl Phys Lett 44:25–27

    Article  CAS  Google Scholar 

  8. Davydov BL, Derkacheva LD, Dunina VV, Zhabotinskii ME, Zolin VF, Koreneva LG, Samokhina MA (1970) Connection between charge transfer and laser second harmonic generation. JETP Lett 12:16–19

    Google Scholar 

  9. Marder SR, Perry JW, Schaefer WP (1989) Synthesis of organic salts with large second-order optical nonlinearities. Science 245:626–628

    Article  CAS  Google Scholar 

  10. Farrusseng D (2011) Metal–organic frameworks: applications from catalysis to gas storage. Wiley-VCH Verlag & Co. KgaA, Weinheim

    Book  Google Scholar 

  11. Evans OR, Lin WB (2002) Crystal engineering of NLO materials based on metal–organic coordination networks. Acc Chem Res 35:511–522

    Article  CAS  Google Scholar 

  12. Wang C, Zhang T, Lin WB (2012) Rational synthesis of noncentrosymmetric metal–organic frameworks for second-order nonlinear optics. Chem Rev 112:1084–1104

    Article  CAS  Google Scholar 

  13. Nickerl G, Henschel A, Grünker R, Gedrich K, Kaskel S (2011) Chiral metal–organic frameworks and their application in asymmetric catalysis and stereoselective separation. Chemie Ingenieur Technik 83:90–103

    Article  CAS  Google Scholar 

  14. Lin WB (2005) Homochiral porous metal–organic framework: why and how? J Solid State Chem 178:2486–2409

    Article  CAS  Google Scholar 

  15. Morris RE, Bu X (2010) Induction of chiral porous solids containing only achiral building blocks. Nat Chem 2:353–361

    Article  CAS  Google Scholar 

  16. Lin JD, Long XF, Lin P, Du SW (2010) A series of cation-templated, polycarboxylate-based Cd(II) or Cd(II)/Li(I) frameworks with second-order nonlinear optical and ferroelectric properties. Cryst Growth Des 10:146–157

    Article  CAS  Google Scholar 

  17. Lin JD, Wu ST, Li ZH, Du SW (2010) Syntheses, topological analyses, and NLO-active properties of new Cd(II)/M(II) (M = Ca, Sr) metal–organic frameworks based on R-isophthalic acids (R = H, OH, and t-Bu). Dalton Trans 39:10719–10728

    Article  CAS  Google Scholar 

  18. Zhao H, Qu ZR, Ye HY, Xiong RG (2008) In situ hydrothermal synthesis of tetrazole coordination polymers with interesting physical properties. Chem Soc Rev 37:84–100

    Article  Google Scholar 

  19. Wang YT, Fan HH, Wang HZ, Chen XM (2005) Homochiral helical wavelike (4,4) networks constructed by divalent metal ions and S-carboxymethyl-l-cysteine. J Mol Struct 740:61–67

    Article  CAS  Google Scholar 

  20. Xu W, Liu W, Yao FY, Zheng YQ (2011) Synthesis, crystal structure and properties of the novel chiral 3D coordination polymer with S-carboxymethyl-l-cysteine. Inorg Chim Acta 365:297–301

    Article  CAS  Google Scholar 

  21. Liang XQ, Li DP, Li CH, Zhou XH, Li YZ, Zuo JL, You XZ (2010) Syntheses, structures, and physical properties of camphorate coordination polymers controlled by semirigid auxiliary ligands with variable coordination positions and conformations. Cryst Growth Des 10:2596–2605

    Article  CAS  Google Scholar 

  22. Zhao H, Li YH, Wang XS, Qu ZR, Wang LZ, Xiong RG, Abrahams BF, Xue Z (2004) Noncentrosymmetric organic solids with very strong harmonic generation response. Chem Eur J 10:2386–2390

    Article  CAS  Google Scholar 

  23. Ye Q, Li YH, Song YM, Huang XF, Xiong RG, Xue Z (2005) A second-order nonlinear optical material prepared through in situ hydrothermal ligand synthesis. Inorg Chem 44:3618–3625

    Article  CAS  Google Scholar 

  24. Ye Q, Tang YZ, Wang XS, Xiong RG (2005) Strong enhancement of second-harmonic generation (SHG) response through multi-chiral centers and metal-coordination. Dalton Trans 1570–1573

    Google Scholar 

  25. Ye Q, Li YH, Wu Q, Song YM, Wang JX, Zhao H, Xiong RG, Xue Z (2005) The first metal (Nd3+, Mn2+, and Pb2+) coordination compounds of 3,5-dinitrotyrosine and their nonlinear optical properties. Chem Eur J 11:988–994

    Article  CAS  Google Scholar 

  26. Anthony SP, Radhakrishnan TP (2004) Helical and network coordination polymers based on a novel C2-symmetric ligand: SHG enhancement through specific metal coordination. Chem Commun 1058–1059

    Google Scholar 

  27. Anthony SP, Radhakrishnan TP (2004) Coordination polymers of Cu(I) with a chiral push-pull ligand: Hierarchical network structures and second harmonic generation. Cryst Growth Des 4:1223–1227

    Article  CAS  Google Scholar 

  28. Evans OR, Xiong RG, Wang Z, Wong GK, Lin W (1999) Crystal engineering of acentric diamondoid metal–organic coordination networks. Angew Chem Int Ed 38:536–538

    Article  CAS  Google Scholar 

  29. Evans OR, Lin W (2001) Crystal engineering of nonlinear optical materials based on interpenetrated diamondoid coordination networks. Chem Mater 13:2705–2712

    Article  CAS  Google Scholar 

  30. Lin W, Ma L, Evans OR (2000) NLO-active zinc(II) and cadmium(II) coordination networks with 8-fold diamondoid structures. Chem Commun 2263–2264

    Google Scholar 

  31. Fu DW, Zhang W, Xiong RG (2008) The first metal–organic framework (MOF) of imazethapyr and its SHG, piezoelectric and ferroelectric properties. Dalton Trans 3946–3948

    Google Scholar 

  32. Ledoux I, Zyss J, Siegel JS, Brienne J, Lehn JM (1990) Second-harmonic generation from non-dipolar non-centrosymmetric aromatic charge-transfer molecules. Chem Phys Lett 172:440–444

    Article  CAS  Google Scholar 

  33. Lin W, Wang Z, Ma L (1999) A novel octupolar metal–organic NLO mateiral based on a chiral 2D coordination network. J Am Chem Soc 121:11249–11250

    Article  CAS  Google Scholar 

  34. Liu Y, Li G, Li X, Cui Y (2007) Cation-dependent nonlinear optical behavior in an octupolar 3D anionic metal–organic open framework. Angew Chem Int Ed 46:6301–6304

    Article  CAS  Google Scholar 

  35. Lin W, Evans OR, Xiong RG, Wang Z (1998) Supramolecular engineering of chiral and acentric 2D networks. Synthesis, structures, and second-order nonlinear optical properties of bis(nicotinato)zinc and bis{3-[2-(4-pyridyl)ethenyl]benzoato} · cadmium. J Am Chem Soc 120:13272–13273

    Article  CAS  Google Scholar 

  36. Evans OR, Lin W (2001) Rational design of nonlinear optical materials based on 2D coordination networks. Chem Mater 13:3009–3017

    Article  CAS  Google Scholar 

  37. He YH, Lan YZ, Zhan CH, Feng YL, Su H (2009) A stable second-order NLO and luminescent Cd(II) complex based on 6-hydroxynicotinic acid. Inorg Chim Acta 362:1952–1956

    Article  CAS  Google Scholar 

  38. Shi JM, Xu W, Liu QY, Liu FL, Huang ZL, Lei H, Yu WT, Fang Q (2002) Polynitrile-bridged two-dimensional crystal: Eu(III) complex with strong fluorescence emission and NLO property. Chem Commun 756–757

    Google Scholar 

  39. Han L, Hong M, Wang R, Luo J, Lin Z, Yuan D (2003) A novel nonlinear optically active tubular coordination network based on two distinct homo-chiral helices. Chem Commun 2580–2581

    Google Scholar 

  40. Hu S, Zou HH, Zeng MH, Wang QX, Liang H (2008) Molecular packing variation of crimpled 2D layers and 3D uncommon 65 · 8 topology: effect of ligand on the construction of metal-quinoline-6-carboxylate polymers. Cryst Growth Des 8:2346–2351

    Article  CAS  Google Scholar 

  41. Zhou WW, Chen JT, Xu G, Wang MS, Zou JP, Long XF, Wang GJ, Guo GC, Huang JS (2008) Nonlinear optical and ferroelectric properties of a 3-D Cd(II) triazolate complex with a novel (63)2(610 · 85) topology. Chem Commun 2762–2764

    Google Scholar 

  42. Yang H, Sang RL, Xu X, Xu L (2013) An unprecedented 3-D SHG MOF material of silver(I) induced by chiral triple helices. Chem Commun 49:2909–2911

    Article  CAS  Google Scholar 

  43. Yu J, Cui Y, Wu C, Yang Y, Wang Z, O’Keeffe M, Chen B, Qian G (2012) Second-order nonlinear optical activity induced by ordered dipolar chromophores confined in the pores of an anionic metal–organic framework. Angew Chem Int Ed 51:10542–10545

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We acknowledge the financial supports from the National Basic Research Program of China (973 Program, 2012CB821702), the National Natural Science Foundation of China (21233009 and 21173221) and the State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences.

Author information

Authors and Affiliations

  1. Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou, 350002, P. R. China

    Shaowu Du & Huabin Zhang

Authors
  1. Shaowu Du
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Huabin Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Shaowu Du .

Editor information

Editors and Affiliations

  1. Department of Chemistry, University of Texas at San Antonio, San Antonio, Texas, USA

    Banglin Chen

  2. Dpt. of Materials Science & Engineering, Zhejiang University, Hangzhou, China

    Guodong Qian

Rights and permissions

Reprints and permissions

Copyright information

© 2013 Springer-Verlag Berlin Heidelberg

About this chapter

Cite this chapter

Du, S., Zhang, H. (2013). Metal–Organic Frameworks for Second-Order Nonlinear Optics. In: Chen, B., Qian, G. (eds) Metal-Organic Frameworks for Photonics Applications. Structure and Bonding, vol 157. Springer, Berlin, Heidelberg. https://doi.org/10.1007/430_2013_107

Download citation

Publish with us

Policies and ethics

Search

Navigation