Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2025 Apr 30;46(11):e70105.
doi: 10.1002/jcc.70105.

Giant Dipole Moments: Remarkable Effects Mono-, Di-, and Tri- Hydrated 5,6-Diaminobenzene-1,2,3,4-Tetracarbonnitrile

Katherine Stanley  1 , R Houston Givhan  1 , Justin M Turney  1 , Henry F Schaefer 3rd  1
Affiliations

Giant Dipole Moments: Remarkable Effects Mono-, Di-, and Tri- Hydrated 5,6-Diaminobenzene-1,2,3,4-Tetracarbonnitrile

Katherine Stanley et al. J Comput Chem. .

Abstract

The molecule 5,6-diaminobenzene-1,2,3,4-tetracarbonnitrile (MOI) was first synthesized by Müllen and coworkers in 2016 and boasts an ultrastrong dipole moment of 14.1 ± 0.7 $$ 14.1\pm 0.7 $$ Debye in THF. Gas phase DFT computations do not fully reflect this ultrastrong dipole moment, demonstrating the role of solvent in increasing this dipole moment. Here, we investigate the effect of solvent molecule position on the dipole moment of this species, computationally examining systems with giant dipole moments. These systems are optimized in the gas phase with the B3LYP functional, employing the aug-cc-pVTZ and def2-TZVP basis sets, as well as the B3LYP-D3BJ/aug-cc-pVTZ functional in Orca. Single point DLPNO-CCSD/aug-cc-pVDZ results were obtained from Orca and Psi4, as well as DLPNO-CCSD(T)/CBS information from Psi4. Additionally, these are compared to the dipole moments of di- and tri-hydrated systems, and the SMD models for THF and water at the B3LYP/aug-cc-pVTZ level of theory. The dissociation energies, HOMO-LUMO energy gaps, and dipole moments are presented. These metrics show the nh1nh1' THF system boasts the largest dissociation energy and dipole moment of the singly solvated systems, due to its strong hydrogen bonding. The importance of solvent placement is highlighted and may guide the synthesis of macromolecules or organic frameworks incorporating the MOI or MOI-like subunits. Remarkably, a single solvent molecule provides a good model for the difference between the gas phase and solvated species. The predicted gas phase dipole moments computed with B3LYP/aug-cc-pVTZ for the MOI, its monohydrated complex, dihydrated complex, and its trihydrated complex are 9.6, 14.2, 16.0, and 16.8 Debye, respectively.

Keywords: dipole; energies; hydrogen bonding; solvent.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflicts of interest.

Figures

FIGURE 1
FIGURE 1
Systems of the MOI with one attached water molecule were examined: (a) nh1, (b) nh1nh1′, (c) cn2, (d) cn2cn2′.
FIGURE 2
FIGURE 2
Systems of the MOI with one attached THF molecule were also examined: (a) nh1, (b) nh1nh1′, (c) cn2, (d) cn2cn2′, (e) ring.
FIGURE 3
FIGURE 3
Dihedral angles of the MOI presented in Table 1 are highlighted here in red. Each dihedral describes the four adjacent carbon atoms on the ring of the MOI.
FIGURE 4
FIGURE 4
Dihedral angles of the MOI presented in Table 2 highlighted in red. Each dihedral contains two adjacent substituents of the MOI with the respective carbon atoms on the ring.
FIGURE 5
FIGURE 5
Directions of dipole moments in the one water systems. Not reflective of magnitude. (a) nh1, (b) nh1nh1′, (c) cn2, (d) cn2cn2′.
FIGURE 6
FIGURE 6
Directions of dipole moments in the THF systems. Not reflective of magnitude. (a) nh1, (b) nh1nh1′, (c) cn2, (d) cn2cn2′, (e) ring.
FIGURE 7
FIGURE 7
Indexing for atomic distances displayed in Table 11.
FIGURE 8
FIGURE 8
Doubly solvated water systems, dipole moment computed at the B3LYP/aug‐cc‐pVTZ level of theory: (a) 16.0 Debye, (b) 14.1 Debye, (c) 10.2 Debye, (d) 9.4 Debye.
FIGURE 9
FIGURE 9
Triply solvated water systems, dipole moment computed at the B3LYP/aug‐cc‐pVTZ level of theory: (a) 16.8 Debye, (b) 15.0 Debye, (c) 12.7 Debye.
FIGURE 10
FIGURE 10
Doubly solvated THF system, dipole moment computed at the B3LYP/aug‐cc‐pVTZ level of theory: (a) 16.3 Debye.
See this image and copyright information in PMC

References

    1. Buckingham A. D., “Molecular Quadrupole Moments,” Quarterly Reviews, Chemical Society 13 (1959): 183–214.
    1. Riley K. E. and Hobza P., “On the Importance and Origin of Aromatic Interactions in Chemistry and Biodisciplines,” Accounts of Chemical Research 46 (2013): 927–936. - PubMed
    1. Horiuchi S. and Tokura Y., “Organic Ferroelectrics,” Nature Materials 7 (2008): 357–366. - PubMed
    1. Liao Y., Firestone K. A., Bhattacharjee S., et al., “Linear and Nonlinear Optical Properties of a Macrocyclic Trichromophore Bundle With Parallel‐Aligned Dipole Moments,” Journal of Physical Chemistry B 110 (2006): 5434–5438. - PubMed
    1. Laidler K. J. and Landskroener P. A., “The Influence of the Solvent on Reaction Rates,” Transactions of the Faraday Society 52 (1956): 200.

LinkOut - more resources