Abstract
A number of superalkali (M3O / M3S; M = Li, Na, K)-doped borazine and hexalithio borazine complexes are considered for the theoretical study of their electronic structure and quadratic polarizability. Electron-rich O/S atom of superalkali species remains very close to one boron atom of the ring through non-covalent interaction. The first-hyperpolarizability increases rather significantly upon superalkali doping. The chosen complexes possess diffuse excess electron which is located on the superpalkali moiety of borazine complexes and at the ring site of lithiated borazines. First-hyperpolarizability of M3O(S)@B3N3Li6 complexes are significantly larger than that of the corresponding M3O(S)@B3N3H6 complexes. The magnitude of first-hyperpolarizability of Li3S@B3N3Li6 is larger than that of Li3S@B3N3H6 by about three orders of magnitude.
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Kanis DR, Ratner MA, Marks TJ (1994) Design and construction of molecular assemblies with large second-order optical nonlinearities. Quantum chemical aspects. Chem Rev 94:195–242
He GS, Tan L-S, Zheng Q, Prasad PN (2008) Multiphoton absorbing materials: molecular designs, characterizations, and applications. Chem Rev 108:1245–1330
Dalton LR, Steier WH, Robinson BH, Zhang C, Ren A, Garner S, Chen A, Londergan T, Irwin L, Carlson B et al (1999) From molecules to opto-chips: Organic electro-optic materials. J Mater Chem 9:1905–1920
Bredas JL, Adant C, Tackx P, Persoons A, Pierce BM (1994) Third-Order Nonlinear Optical Response in Organic Materials: Theoretical and Experimental Aspects. Chem Rev 94:243–278
Marder SR, Torruellas WE, Blanchard-Desce M, Ricci V, Stegeman GI, Gilmour S, Bre’das JL, Li J, Bublitzand GU, Boxer SG (1997) Large Molecular Third-Order Optical Nonlinearities in Polarized Carotenoids. Science 276:1233
Chen A, Murphy EJ (2012) Broadband Optical Modulators: Science,Technology. and Applications. CRC Press/Taylor & Francis Group, Boca Raton
Nakano M, Fujita H, Takahata M, Yamaguchi K (2002) Theoretical study on second hyperpolarizabilities of phenylacetylene dendrimer: toward an understanding of structure−property relation in NLO responses of fractal antenna dendrimers. J Am Chem Soc 124:9648–9655
Reed GT, Mashanovich G, Gardes FY, Thomson DJ (2010) Silicon optical modulators. Nat Photonics 4:518–526
Jiang N, Zuber G, Keinan S, Nayak A, Yang W, Therien MJ, Beratan DN (2012) Design of coupled porphyrin chromophores with unusually large hyperpolarizabilities. J Phys Chem C116:9724–9733
Cesaretti A, Foggi P, Fortuna CG, Elisei F, Spalletti A, Carlotti B (2020) Uncovering structure−property relationships in push−pull chromophores: a promising route to large hyperpolarizability and two−photon absorption. J Phys Chem C 124(29):15739–15748
Wang Y-F, Qin T, Tang J-M, Liu Y-J, Xie M, Li J, Huang J, Li Z-R (2020) Novel inorganic aromatic mixed-valent superalkali electride CaN3Ca: an alkaline-earth-based high-sensitivity multi-state nonlinear optical molecular switch. Phys Chem Chem Phys 22:5985–5994
Roy RS, Mondal A, Nandi PK (2017) First hyperpolarizability of cyclooctatetraene modulated by alkali and alkaline earth metals. J Mol Model 23:93
Desce MB, Alain V, Midrier L, Wortmann R, Lebus S, Glania C, Kramer P, Fort A, Muller J, Barzoukas M (1997) Intramolecular charge transfer and enhanced quadratic optical non-linearities in push pull polyenes. J Photochem Photobiol A 105:115–121
Roy RS, Nandi PK (2015) Exploring bridging effect on first hyperpolarizability. RSC Adv 5:103729–103738
Meyers F, Marder SR, Pierce BM, Bredas JL (1994) Electric Field Modulated Nonlinear Optical Properties of Donor-Acceptor Polyenes: Sum-Over-States Investigation of the Relationship between Molecular Polarizabilities (.alpha., .beta., and .gamma.) and Bond Length Alternation. J Am Chem Soc 116:10703–10714
Bai Y, Zhou Z-J, Wang J-J, Li Y, Wu D, Chen W, Li Z-R, Sun C-C (2013) New Acceptor–Bridge–Donor Strategy for Enhancing NLO Response with Long-Range Excess Electron Transfer from the NH2...M/M3O Donor (M = Li, Na, K) to Inside the Electron Hole Cage C20F19 Acceptor through the Unusual σ Chain Bridge (CH2)4. J Phys Chem A 117:2835–2843
Roy RS, Nandi PK (2018) Electronic structure and large second-order non-linear optical property of COT derivatives – a theoretical exploration. Phys Chem Chem Phys 20:18744–18755
Chen W, Li ZR, Wu D, Li Y, Sun CC, Gu FL, Aoki Y (2006) Nonlinear optical properties of alkalides Li+(calix[4]pyrrole)M- (M = Li, Na, and K): alkali anion atomic number dependence. J Am Chem Soc 128:1072–1073
Nakano M, Fukuda K, Champagne B (2016) Third-Order Nonlinear Optical Properties of Asymmetric Non-Alternant Open-Shell Condensed-Ring Hydrocarbons: Effects of Diradical Character, Asymmetricity, and Exchange Interaction. J Phys Chem C 120(2):1193–1207
Okuno K, Shigeta Y, Kishi R, Nakano M (2013) Photochromic switching of diradical character: design of efficient nonlinear optical switches. J Phys Chem Lett 4:2418–2422
Chen W, Li ZR, Wu D, Li Y, Sun CC, Gu FL (2005) The structure and the large nonlinear optical properties of Li@calix[4]pyrrole. J Am Chem Soc 127:10977–10981
Muhammad S, Xu HL, Liao Y, Kan YH, Su ZM (2009) Quantum mechanical design and structure of the Li@B10H14 basket with a remarkably enhanced electro-optical response. J Am Chem Soc 131:11833–11840
Silveira O, Castro MA, Leão SA, Fonseca TL (2015) Second hyperpolarizabilities of the lithium salt of pyridazine Li–H3C4N2 and lithium salt electride Li–H3C4N2⋯Na2. Chem Phys Lett 633:241–246
Li ZJ, Li ZR, Wang FF, Luo C, Ma F, Wu D, Wang Q, Huang XR (2009) A Dependence on the Petal Number of the Static and Dynamic First Hyperpolarizability for Electride Molecules: Many-Petal-Shaped Li-Doped Cyclic Polyamines. J Phys Chem A113:2961–2966
Marques S, Castro MA, Leão SA, Fonseca TL (2018) Electronic and vibrational hyperpolarizabilities of lithium substituted (Aza)benzenes and (Aza)naphthalenes. J Phys Chem A 122:7402–7412
Sun W-M, Wu D, Li Y, Liu JY, He HM, Li ZR (2015) A theoretical study on novel alkaline earth-based excess electron compounds: unique alkalides with considerable nonlinear optical responses. Phys Chem Chem Phys 17:4524–4532
Raptis SG, Papadopoulas MG, Sadlej A (2000) Hexalithiobenzene: a molecule with exceptionally high second hyperpolarizability. Phys Chem Chem Phys 2:3393–3399
Xu H-L, Li Z-R, Wu D, Ma F, Li Z-J, Gu FL (2009) Lithiation and Li-doped effects of [5]Cyclacene on the static first hyperpolarizability. J Phys Chem C 113:4984–4986
Zhong R-L, Sun S-L, Xu H-L, Qiu Y-Q, Su Z-M (2014) Multilithiation effect on the first hyperpolarizability of carbon–boron–nitride heteronanotubes: activating segment versus connecting pattern. J Phys Chem C118:14185–14191
Khanna SN, Jena P (1995) Atomic clusters: building blocks for a class of solids. Phys Rev B: Condens Matter Mater Phys 51:13705–13716
Gutsev GL, Boldyrev AI (1982) DVM Xα calculations on the electronic structure of “superalkali” cations. Chem Phys Lett 92:262–266
Kerr JA (2000) CRC handbook of chemistry and physics. CRC Press, Boca Raton
Lin Z, Lu T, Ding X-L (2017) A theoretical investigation on doping superalkali for triggering considerable nonlinear optical properties of Si12C12 nanostructure. J Comput Chem 38:1574–1582
Li Z, Yu G, Zhang X, Huang X, Chen W (2017) Bonding the superalkali M3O (M = Li and K): an effective strategy to improve the electronic and nonlinear optical properties of the inorganic B40 nanocage. Phys E 94:204–210
Wu CH, Kudoa H, Ihle HR (1979) Thermochemical properties of gaseous Li3O and Li2O2. J Chem Phys 70:1815–1820
Kudo H, Yokoyama K, Wu CH (1994) The stability and structure of the hyperlithiated molecules Li3S and Li4S: an experimental and ab initio study. J Chem Phys 101:4190
Sun W-M, Li X–H, Wu D, Li Y, He H–M, Li Z–R, Chena J–H, Li C–Y (2016) A theoretical study on superalkali-doped nanocages: unique inorganic electrides with high stability, deep-ultraviolet transparency, and a considerable nonlinear optical response. Dalton Trans 45:7500–7509
Zhang F–Y, Xu H–L, Su Z–M (2017) Superatoms-induced effects of phenalenyl π-dimer on NICS and NLO properties: not always enhancement. J Phys Chem C 121(37):20419–20425
Dabbagh HA, Shahraki M, Farrokhpour H (2014) Theoretical investigation of the borazine–melamine polymer as a novel candidate for hydrogen storage applications. Phys Chem Chem Phys 16:10519
Schröder M (2010) Functional metal-organic frameworks: gas storage, Separation and Catalysis. Springer, Berlin
Sham IHT, Kwok CC, Che CM, Zhu N (2005) Borazine materials for organic optoelectronic applications. Chem Commun (Camb) 28:3547
Bosdet MJD, Piers WE, Sorensen TS, Parvez M (2007) 10a-Aza-10b-borapyrenes: heterocyclic analogues of pyrene with internalized BN moieties. Angew Chem Int Ed 46:4940
Dewar MJS, Kubba VP, Pettit R (1958) New heteroaromatic compounds. Part I. 9-Aza-10-boraphenanthrene. J Chem Soc 0:3073–3076
Campbell PG, Marwitz AJV, Liu S-Y (2012) Recent Advances in Azaborine Chemistry. Angew Chem Int Ed 51:6074
Otero N, Pouchan C, Karamanis P (2017) Quadratic nonlinear optical (NLO) properties of borazino (B3N3)-doped nanographenes. J Mater Chem C 5:8273–8287
Wang L, Wang W-Y, Qiu Y-Q, Lu H-Z (2015) Second-Order Nonlinear Optical Response of Electron Donor–Acceptor Hybrids Formed between Corannulene and Metallofullerenes. J Phys Chem C 119:24965–24975
Xu H-L, Li Z-R, Wu D, Wang B-Q, Li Y, Gu FL, Aoki Y (2007) Structures and Large NLO Responses of New Electrides: Li-Doped Fluorocarbon Chain. J Am Chem Soc 129:2967–2970
Sarmah N, PKr B, Bania KK (2014) Substituent and solvent effects on the absorption spectra of cation−π complexes of benzene and Borazine: a theoretical study. J Phys Chem A 118:3760–3774
Srivastava AK, Tiwari SN, Misra N (2017) Alkalized borazine: a simple recipe to design closed-shell superalkalis. Int J Quantum Chem 118:e25507
Baran JR, Hendrickson JC, Laude DA, Lagow JRJ (1992) Synthesis of hexalithiobenzene. J Organomet Chem 57:3759–3760
Becke AD (1993) Density-functional thermochemistry III. The role of exact exchange. J Chem Phys 98:5648–5652
Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B Condens Matter 37:785–789
Lisovenko AS, Timoshkin AY (2010) Donor−acceptor complexes of borazines. Inorg Chem 49:10357–10369
Loh KP, Yang SW, Soon JM, Zhang H, Wu P (2003) Ab Initio Studies of Borazine and Benzene Cyclacenes and Their Fluoro-Substituted Derivatives. J Phys Chem A 107:5555–5560
Deshmukh V, Nagnathappa M, Kharat B, Chaudhari A (2014) Theoretical study of borazine and substituted borazines using density functional theory method. J Mol Liq 193:13–22
Gu J, Le Y-Q, Hu Y-Y, Li W-Q, Tian WQ (2014) Tuning the First Hyperpolarizabilities of Boron Nitride Nanotubes. ACS Photonics 1:928–935
Boyd RJ, Choi SC, Hale CC (1984) Electronic and structural properties of borazine and related molecules. Chem Phys Lett 112:136–141
Chakraborty A, Bandaru S, Das R, Duley S, Giri S, Goswami K, Mondal S, Pan S, Sena S, Chattaraj PK (2012) Some novel molecular frameworks involving representative elements. Phys Chem Chem Phys 14:14784–14802
Giri S, Behera S, Jena P (2014) Superalkalis and superhalogens as building blocks of supersalts. J Phys Chem A 118:638–645
Reed AE, Curtiss LA, Weinhold F (1988) Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chem Rev 88:899–926
Bader RFW (1990) Atoms in molecules: a quantum theory. Oxford University Press, Oxford
Chai JD, Gordon MH (2008) Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections. Phys Chem Chem Phys 10:6615–6620
Ye J-T, Wang L, Wang H–Q, Chen Z–Z, Qiu Y–Q, Xie H-M (2017) Spirooxazine molecular switches with nonlinear optical responses as selective cation sensors. RSC Adv 7:642–650
Chakraborty D, Chattaraj PK (2016) Optical response and gas sequestration properties of metal cluster supported graphene nanoflakes. Phys Chem Chem Phys 18:18811–18827
Iikura H, Tsuneda T, Yanai T, Hirao K (2001) A long-range correction scheme for generalized-gradient-approximation exchange functionals. J Chem Phys 115:3540–3544
Ullah F, Kosar N, Ayub K, Gilani MA, Mahmood T (2019) Theoretical study on a boron phosphide nanocage doped with superalkalis: novel electrides having significant nonlinear optical response. New J Chem 43:5727–5736
Hatua K, Mondal A, Nandi KP (2017) Static second hyperpolarizability of diffuse electron compound M2X (M = Li, na; X = H, F): Ab-initio study of basis set effect and electron correlation. Chem Phys Lett 686:1–6
Oudar JL, Chemla DS (1977) Hyperpolarizabilities of the nitroanilines and their relations to the excited state dipole moment. J Chem Phys 66:2664–2668
Wang J-J, Zhou Z–J, Bai Y, Liu Z-B, Li Y, Wu D, Chen W, Li Z-R, Sun C–C (2012) The interaction between superalkalis (M3O, M = Na, K) and a C20F20 cage forming superalkali electride salt molecules with excess electrons inside the C20F20 cage: dramatic superalkali effect on the nonlinear optical property. J Mater Chem 22:9652–9657
Huang S, Liao K, Peng B, Luo Q (2016) On the Potential of Using the Al7 Superatom as an Excess Electron Acceptor To Construct Materials with Excellent Nonlinear Optical Properties. Inorg Chem 55:4421–4427
Islam N, Chimni SS (2016) DFT investigation on nonlinear optical (NLO) properties of novel borazine derivatives. Comput Theor Chem 1086:58–66
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA et al (2009) Gaussian 09, revision B. Gaussian, Inc., Wallingford, p 02
Bader RFW (1994) Atoms in molecules. A quantum theory. Clarendon Press, Oxford
Gibbs GV, Boisen MB, Beverly LL, Rosso KM (2001) A computational quantum chemical study of the bonded interactions in earth materials and structurally and chemically related molecules. In: Cygan RT, Kubicki JD (eds) Molecular Modeling Theory: Applications in the Geosciences, vol 42. Mineralogical Society of America, Washington, p 345
Banerjee P, Hatua K, Mondal A, Nandi PK (2019) Substituent effects at nitrogen/phosphorus atoms of dialkaline earth metal complexes: excess electron and large second-hyperpolarizability. Int J Quantum Chem 119:1–15
Mondal A, Hatua K, Roy RS, Nandi PK (2017) Successive lithiation of acetylene, ethylene and benzene: a comprehensive computational study of large static second hyperpolarizability. Phys Chem Chem Phys 19:4768
Mayers F, Marder SR, Perry JW (1998) Introduction to the nonlinear optical properties of organic materials. In: Interrante LV, Hampden-Smith MJ (eds) Chemistry of advanced materials. Wiley-VCH, New York, pp 207–269
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All authors contributed to the present work by giving their own conception and design. The computational tasks, tabulation of results, and appropriate theoretical justification/analysis were performed by Ria Sinha Roy, Subhadip Ghosh and Kaushik Hatua. The manuscript in the final form was checked and prepared by Ria Sinha Roy and Prasanta K. Nandi. All authors gave their specific scientific inputs and suggestions to improve the quality of the manuscript. All authors read and approved the final manuscript.
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The geometrical parameters, NBO calculated atomic charges, mean polarizability, first- hyperpolarizability and TDDFT calculated results are reported in Tables S1, S2, S3, S4, S5, S6, S7, S8, S9 and S10, respectively. The optimized structures of superalkali species are shown in Fig. S1 in this section. (DOCX 94 kb) (DOCX 94 kb)
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Roy, R.S., Ghosh, S., Hatua, K. et al. Superalkali-doped borazine and lithiated borazine complexes: diffuse excess electron and large first-hyperpolarizability. J Mol Model 27, 74 (2021). https://doi.org/10.1007/s00894-021-04688-2
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DOI: https://doi.org/10.1007/s00894-021-04688-2