Abstract
Due to its distinctive properties and semiconducting characteristics, B12N12 has been the subject of many studies in the field of nanoscience, as it is a promising material for various applications, such as in electronics, catalysts, optoelectronic sensors and energy storage. In addition, the modification of B12N12 with transition metals (TM) increases its potential. Techniques such as charge decomposition analysis (CDA), UV–Vis spectroscopy, circular dichroism (CD), molecular dynamics (MD) and work function study (Φ) are applied in this work in order to investigate the dynamics of charge transfers, optical properties, chirality, electronic transitions and thermodynamic stability of pure and TM-modified B12N12. The calculations were developed at DFT-D3 and TD-DFT level with the B3LYP/6-31G(d,p) basis set. The CDA results showed that the charge transfer’s predominant direction is from the cage to the TM, and that, in general, the charge donation effect is greater than the back-donation. The UV–Vis spectra analysis shows that pure B12N12 absorbs in the IR region, while modification with TM shifts the absorption peaks to the visible region in some cases. We observed that the presence of TM caused deformations in the structure of some nanocages, which began to show chirality as well as CD and g-factor signals. Molecular dynamics revealed that B12N12 and most of the modified nanocages are stable systems, but some changes in configuration were observed. The work function analysis indicated specific nanocages’ potential in work function sensor applications.
Graphical Abstract
Similar content being viewed by others
Data Availability
No datasets were generated or analysed during the current study.
References
D. Gonzalez-Ortiz, C. Salameh, M. Bechelany, P. Miele, Nanostructured boron nitride-based materials: synthesis and applications. Mater. Today Adv. 8, 100107 (2020)
Y. Arshad, M. Asghar, M. Yar, T. Bibi, K. Ayub, Transition metal doped boron nitride nanocages as high performance nonlinear optical materials: A DFT study. J. Inorg. Organomet. Polym. Mater. 33, 943–955 (2023)
A.L.P. Silva, N.S. Sousa, J.J.G. Varela Júnior, Theoretical studies with B12N12 as a toxic gas sensor: a review. J. Nanoparticle Res. 25, 22 (2023)
T. Oku, A. Nishiwaki, I. Narita, Formation and atomic structure of B12N12 nanocage clusters studied by mass spectrometry and cluster calculation. Sci. Technol. Adv. Mater. 5, 635–645 (2004)
T. Oku, T. Hirano, M. Kuno, T. Kusunose, K. Niihara, K. Suganuma, Synthesis, atomic structures and properties of carbon and boron nitride fullerene materials. Mater. Sci. Eng. B 74, 206–217 (2000)
T. Oku, M. Kuno, H. Kitahara, I. Narita, Formation, atomic structures and properties of boron nitride and carbon nanocage fullerene materials. Int. J. Inorg. Mater. 3, 597–612 (2001)
T. Oku, I. Narita, A. Nishiwaki, N. Koi, Atomic structures, electronic states and hydrogen storage of boron nitride nanocage clusters. Nanotubes and Nanohorns. Defect. Diffus. Forum 226, 113–140 (2004)
X. Zhang, L. Kang, M. Zhu, Density functional theory study of low-dimensional (2D, 1D, 0D) boron nitride nanomaterials catalyzing acetylene acetate reaction. Int. J. Mol. Sci. 23, 9997 (2022)
A.R. Ayub, U. Yaqoob, S. Rafiq, R.A. Shehzad, K. Ayub, J. Iqbal, H. Li, K.H. Mahmoud, K.A. Elsayed, A quantum chemical study of outstanding structural, electronic and nonlinear optical polarizability of boron nitride (B12N12) doped with super salt (P7BaNO3). J. Inorg. Organomet. Polym. Mater. 32, 3738–3764 (2022)
M.Y. Mehboob, R. Hussain, F. Younas, S. Jamil, M.M.A. Iqbal, K. Ayub, N. Sultana, M.R.S.A. Janjua, Computation assisted design and prediction of alkali-metal-centered B12N12 nanoclusters for efficient H2 adsorption: new hydrogen storage materials. J. Clust. Sci. 34, 1237–1247 (2023)
N.P. Shetti, A. Mishra, S. Basu, T.M. Aminabhavi, Versatile fullerenes as sensor materials. Mater. Today Chem. 20, 100454 (2021)
S. Hussain, R. Hussain, M.Y. Mehboob, S.A.S. Chatha, A.I. Hussain, A. Umar, M.U. Khan, M. Ahmed, M. Adnan, K. Ayub, Adsorption of phosgene gas on pristine and copper-decorated B12N12 nanocages: A comparative DFT study. ACS Omega 5, 7641–7650 (2020)
F. Rahimi, A. Zabaradsti, Photo-induced electron transfer process on pristine and Sc-substituted B12N12 nanocage as H2S chemosensor: a fully DFT and TD-DFT study. J. Inorg. Organomet. Polym. 27, 1770–1777 (2017)
A.L.P. Silva, J.J.G. Varela Júnior, MB11N12 (M=Fe-Zn) Nanocages for Cyanogen Chloride Detection: A DFT Study. J. Inorg. Organomet. Polym. Mater. (2023)
H.Y. Ammar, H.M. Badran, Kh.M. Eid, TM-doped B12N12 nanocage (TM = Mn, Fe) as a sensor for CO, NO, and NH3 gases: A DFT and TD-DFT study. Mater. Today Commun. 25, 101681 (2020)
Z. Zhao, Z. Li, Q. Wang, Structures, electronic and magnetic properties of transition metal atoms encapsulated in B12N12 cage. Chem. Phys. Lett. 739, 136922 (2020)
A.L.P. Silva, J.J.G. Varela Júnior, Density Functional Theory Study of Cu-Modified B12N12 Nanocage as a Chemical Sensor for Carbon Monoxide Gas. Inorg. Chem. 62, 1926–1934 (2023)
E. Runge, E.K.U. Gross, Density-functional theory for time-dependent systems. Phys. Rev. Lett. 52, 997–1000 (1984)
S. Kaviani, S. Shahab, M. Sheikhi, V. Potkin, H. Zhou, A DFT study of Se-decorated B12N12 nanocluster as a possible drug delivery system for ciclopirox. Comput. Theor. Chem. 1201, 113246 (2021)
S. Dapprich, G. Frenking, Investigation of donor-acceptor interactions: a charge decomposition analysis using fragment molecular orbitals. J. Phys. Chem. 99, 9352–9362 (1995)
R. Ghiasi, A. Valizadeh, Computational investigation of interaction of a cycloplatinated thiosemicarbazone as antitumor and antiparasitic agents with B12N12 nano-cage. Results Chem. 5, 100768 (2023)
M. Perveen, S. Nazir, A.W. Arshad, M.I. Khan, M. Shamim, K. Ayub, M.A. Khan, J. Iqbal, Therapeutic potential of graphitic carbon nitride as a drug delivery system for cisplatin (anticancer drug): A DFT approach. Biophys. Chem. 267, 106461 (2020)
A.M. Satawara, G.A. Shaikh, S.K. Gupta, P.N. Gajjar, Structural, electronic and optical properties of hexagonal boron-nitride (h-BN) monolayer: An Ab-initio study. Mater. Today: Proc. 47, 529–532 (2020)
E. Vessally, M.D. Esrafili, R. Nurazar, P. Nematollahi, A. Bekhradnia, A DFT study on electronic and optical properties of aspirin-functionalized B12N12 fullerene-like nanocluster. Struct. Chem. 28, 735–748 (2017)
S.A. Jasim, A.H. Shather, T. Alawsi, A.A. Ramírez-Coronel, A.B. Mahdi, M. Normatov, M.J.C. Opulencia, F. Kamali, Adsorption properties of B12N12, AlB11N12, and GaB11N12 nanostructure in gas and solvent phase for phenytoin detecting: A DFT study. Inorg. Chem. Commun. 146, 110158 (2022)
N. Abdolahi, M. Aghaei, A. Soltani, Z. Azmoodeh, H. Balakheyli, F. Heidari, Adsorption of Celecoxib on B12N12 fullerene: Spectroscopic and DFT/TD-DFT study Spectrochim. Acta - Part A: Mol. Biomol. Spectroscopy 204, 348–353 (2018)
MstS Khanom, Md.R Hossain, KZ Islam, MdA Hossain, F Ahmed, First-principles investigation of Hydroxycarbamide anticancer drug delivery by X12N12 (X = B, Al, Ga) fullerene nanostructures: A DFT, NBO and QTAIM analysis. Comput. Theor. Chem. 1216, 113869 (2022)
H.Y. Ammar, Kh.M. Eid, H.M. Badran, The impact of an external electric field on methanol adsorption on XB11N12 (X=B Co, Ni) nanocages: A DFT and TD-DFT study. J. Phys. Chem. Solids 153, 10033 (2021)
H. Jouypazadeh, H. Farrokhpour, DFT and TD-DFT study of the adsorption and detection of sulfur mustard chemical warfare agent by the C24, C12Si12, Al12N12, Al12P12, Be12O12, B12N12 and Mg12O12 nanocages. J. Mol. Struct. 1164, 227–238 (2018)
A.R. Ayub, M. Zeshan, S. Arshad, S. Shafiq, M.U. Kamal, N. Ghani, K. Ayub, S.A.M. Abdelmohsen, M.M. Alanazi, J. Iqbal, Density functional theory (DFT) study of non-linear optical properties of super salt doped boron nitride cage. Diam. Relat. Mater. 137, 110080 (2023)
W. Ma, L. Xu, A.F. Moura, X. Wu, H. Kuang, C. Xu, N.A. Kotov, Chiral Inorganic Nanostructures. Chem. Rev. 117, 8041–8093 (2017)
S. Zhu, M. Sun, Electronic circular dichroism and Raman optical activity: Principle and applications. Appl. Spectrosc. Rev. 56, 553–587 (2021)
R.E. del Río, P. Joseph-Nathan, Vibrational circular dichroism absolute configuration of natural products from 2015 to 2019. Nat. Prod. Commun. 16, 1–30 (2021)
H. Holami, D. Chakraborty, J. Zhang, B. Borhan, Absolute stereochemical determination of organic molecules through induction of helicity in host-guest complexes. Acc. Chem. Res. 54, 654–667 (2021)
Y. Luo, K. Wang, J. Mu, Y. Cai, W. Zhu, Exploring the adsorption behavior of pyrazinamide on the surface of X12Y12 (X = B, Al; Y = N, P) nanocages: A in-silico study. J. Mol. Liq. 372, 121211 (2023)
A. Escobedo-Morales, L. Tepech-Carrillo, A. Bautista-Hernández, J.H. Camacho-García, D. Cortes-Arriagada, E. Chigo-Anota, Effect of chemical order in the structural stability and physicochemical properties of B12N12 fullerenes. Sci. Rep. 9, 16521 (2019)
G.M. Ahangari, A.H. Mashhadzadeh, Density functional theory based molecular dynamics study on hydrogen storage capacity of C24, B12N12, Al12N12, Be12O12, Mg12O12, and Zn12O12 nanocages. Int. J. Hydrogen Energy 45, 6745–6756 (2020)
N.S. Sousa, A.L.P. Silva, A.C.A. Silva, J.J.G. Varela Júnior, DFT Study of Frist How Transition Metals Doped, Encapsulated and Decorated on B12N12 Nanocage: Part 1 - Structural, Energetic and Electronic Properties. J. Inorg. Organomet. Polym. Mater. (2024)
Y. Cao, A. Khan, H. Balakheyli, A.Ng.K. Lup, M.R. Taghartapeh, H. Mirzaei, S.R. Khandoozi, A. Soltani, M. Aghaei, F. Heidari, S.M. Sarkar, A.B. Albadarin, Penicillamine functionalized B12N12 and B12CaN12 nanocages act as potential inhibitors of proinflammatory cytokines: A combined DFT analysis, ADMET and molecular docking study. Arab. J. Chem. 14, 103200 (2021)
Q. Wang, P. Zhang, M.J. Ansari, M.F. Aldawsari, A.S. Alalaiwe, J. Kaur, R. Kumar, A.Ng.K. Lup, A. Enayati, H. Mirzaei, A. Soltani, C.-H. Su, H.C. Nguyen, Electrostatic interaction assisted Ca-decorated C20 fullerene loaded to anti-inflammatory drugs to manage cardiovascular disease risk in rheumatoid arthritis patients. J. Mol. Liq. 350, 118564 (2022)
M. Suliman, M.H. Kzar, A.S.M. Juma, I.A. Ali, Y. Yasin, N.H. Sayyid, A.T. Alkhafaji, A.J. Kadhim, M.M. Abid, A.H. Alawadi, A. Alsalamy, J. Kaurj, E. Tazikeh-Lemeski, S.M. Rad, A. Soltani, B40 and SiB39 fullerenes enhance the physicochemical features of curcumin and effectively improve its anti-inflammatory and anti-cancer activities. J. Mol. Liq. 395, 123816 (2024)
F. Neese, The ORCA program system. Wiley Interdiscip. Rev. Comput. Mol. Sci. 2, 73–78 (2012)
F. Neese, Software update: the ORCA program system, version 4.0. WIREs Comput. Mol. Sci. 8, e1327 (2018)
F. Neese, Software update: The ORCA program system-Version 5.0. WIREs Comput Mol. Sci. 12, e1606 (2022)
S. Grimme, Density functional theory with London dispersion corrections. WIREs Comput. Mol. Sci. 1, 211–228 (2011)
T. Lu, F. Chen, Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 29, 580–592 (2012)
S. Grimme, C. Bannwarth, P. Shushkov, A Robust and Accurate Tight-Binding Quantum Chemical Method for Structures, Vibrational Frequencies, and Noncovalent Interactions of Large Molecular Systems Parametrized for All spd-Block Elements (Z = 1–86). J. Chem. Theory Comput. 13, 1989–2009 (2017)
B.A. Ravan, H. Jafari, DFT study on electronic and optical properties of halogen-adsorbed hexagonal boron nitride. Comput. Condens. Matter. 21, e00416 (2019)
A.R. Juárez, F. Ortiz-Chi, M. Borges-Martínez, G. Cárdenas-Jirón, M.S. Villanueva, E.C. Anota, Stability, electronic and optical properties of the boron nitride cage (B47N53) from quantum mechanical calculations. Phys. E Low-dimens. Syst. Nanostruct. 111, 118–126 (2019)
Y. Shichibu, Y. Ogawa, M. Sugiuchi, K. Konishi, Chiroptical activity of Au13 clusters: experimental and theoretical understanding of the origin of helical charge movements. Nanoscale Adv. 3, 1005–1011 (2021)
P. Pakravan, S.A. Siadati, A [1+2] cycloaddition instead of usual [2+3] cycloaddition between the B12N12 cluster and methyl azide: Potential energy surface calculations and Born-Oppenheimer molecular dynamics simulations. Prog. React. Kinet. Mech. 45, 1–10 (2020)
C.A. Celaya, L.F. Hernandez-Ayala, F.B. Zamudio, J.A. Vargas, M. Reina, Adsorption of melphalan anticancer drug on C24, B12N12, B12C6N6, B6C12N12 and B6C6N12 nanocages: A comparative DFT study. J. Mol. Liq. 329, 115528 (2021)
N.S. Sousa, A.L.P. Silva, A.C.A. Silva, J.J.G. Varela Júnior, Cu-modified B12N12 nanocage as a chemical sensor for nitrogen monoxide gas: a density functional theory study. J. Nanoparticle Res. 25, 248 (2023)
A.L.P. Silva, A.C.A. Silva, J.J.G. Varela Júnior, Putrescine adsorption on pristine and Cu-decorated B12N12 nanocages: a density functional theory study. Comput. Theor. Chem. 1215, 113836 (2022)
A.L.P. Silva, A.C.A. Silva, C.N. Navis, J.J.G. Varela Júnior, Theoretical study of putrescine and X12Y12 (X=Al, B and Y=N, P) nanocage interactions. J. Nanoparticle Res. 23, 108 (2021)
K. Potje-Kamloth, Semiconductor junction gas sensors. Chem. Rev. 1008, 367–399 (2008)
A.L. Smith, R. Breitwieser, Richardson-Dushman equation monograph. J. Appl. Phys. 41, 436–437 (1970)
A. Soltani, M.R. Taghartapeh, V. Erfani-Moghadam, M.B. Javan, F. Heidari, M. Aghaei, P.J. Mahon, Serine adsorption through different functionalities on the B12N12 and PtB12N12 nanocages. Mater. Sci. Eng. C 92, 216–227 (2018)
N. Abdolahi, P. Singla, A. Soltani, M. Javan, M. Aghaei, F. Heidari, S. Sedighi, Gold decorated B12N12 nanocluster as an effective sulfasalazine drug carrier: A theoretical investigation. Phys. E: Low-Dimens. 124, 114296 (2020)
Y. Cao, A. Khan, H. Mirzaei, S.R. Khandoozi, M. Javan, A.Ng.K. Lup, A. Norouzi, E.T. Lemeski, M. Pishnamazi, A. Soltani, A.B. Albadarin, Investigations of adsorption behavior and anti-cancer activity of curcumin on pure and platinum-functionalized B12N12 nanocages. J. Mol. Liq. 334, 116516 (2021)
Acknowledgements
The authors acknowledge financial support by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES—grant No. 88887.472618/2019-00-PROCAD-AM).
Funding
This article was funded by Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, 88887.472618/2019-00-PROCAD-AM.
Author information
Authors and Affiliations
Contributions
Natanael de S. Sousa: Methodology, Data curation, Investigation, Formal analysis, Writing—original draft. Adilson L. P. Silva: Formal analysis, Writing—original draft, Writing—review & editing. Augusto César Azevedo Silva: Formal analysis, Writing—original draft, Writing—review & editing. Jaldyr de J. G. Varela Júnior: Conceptualization, Supervision, Resources, Funding acquisition, Writing—review & editing.
Corresponding authors
Ethics declarations
Conflict of interest
The authors declare that there is no conflict of interest regarding the publication of this article.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
De Sousa Sousa, N., Silva, A.L.P., Silva, A.C.A. et al. DFT Analysis of Dynamic, Charge, and TD-DFT Properties of Doped, Encapsulated, and Decorated First-Row Transition Metals on B12N12 Nanocage: Part 2. J Inorg Organomet Polym (2024). https://doi.org/10.1007/s10904-024-03025-3
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s10904-024-03025-3