Tailoring Molecular Architecture: Charge-transfer Cocrystals Based on TCNQ in Advanced Electrical, Magnetic, and Photo-thermal Applications

doi:10.1007/s40242-025-5220-8

Abstract

Abstract: The discovery of the first TCNQ-based charge-transfer (CT) cocrystal, which is composed of a tetrathiafulvalene (TTF) donor and 7,7,8,8-tetracyanoquinodimethane (TCNQ) acceptor (TTF-TCNQ), sparked a thorough investigation into the fabrication of novel CT cocrystals by combining TCNQ and its derivatives with different donor molecules. Due to the strong intermolecular interactions and tunable stacking modes, TCNQ-based cocrystals display unique properties, including ambipolar transport, low-temperature ferromagnetism, and red-shifted optical absorption. However, to achieve precise control of cocrystal growth, morphology, and electronic functionality remains a big challenge. In this review, we mainly focus on fundamental concepts of TCNQ-based CT cocrystals, such as types of interactions, stacking modes, methods for tuning properties, and techniques for growing high-quality crystals. Furthermore, their applications in electronics, magnetism, and emerging photothermal technologies, such as imaging, therapy, and desalination are highlighted.

Key words: Organic cocrystal, Charge-transfer, 7,7,8,8-Tetracyanoquinodimethane (TCNQ), Crystal engineering, Optoelectronics, Photothermal conversion

ZIKAR E ISLAM Muhammad, DU Shaolin, LI Tingting, SUN Shiyue, KE Yunzhe, JIA Bao, SUN Lingjie, ZHANG Xiaotao, DING Shuaishuai. Tailoring Molecular Architecture: Charge-transfer Cocrystals Based on TCNQ in Advanced Electrical, Magnetic, and Photo-thermal Applications[J]. Chemical Research in Chinese Universities, 2025, 41(6): 1348-1374.

References

[1] Zhu W., Zhang X., Hu W., Science Bulletin, 2021, 66, 512.
[2] Ostroverkhova O., Chemical Reviews, 2016, 116, 13279.
[3] Nowsherwan G. A., Ali Q., Ali U. F., Ahmad M., Khan M., Hussain S. S., Organics, 2024, 5, 520.
[4] Xin M., Yu T., Jiang Y., Tao R., Li J., Ran F., Zhu T., Huang J., Zhang J., Zhang J. H., Hu N., Wang W., Zhang Q., Liu Z., Wang X., Shi Y., SmartMat, 2023, 4, e1157.
[5] Ji J., Yang B., Zhang C., Cai Y., Chen J., Zhao C., Wang T., Wu L., Liu M., Bai J., Wang J., Wu Z., Chen S., Ling H., An Z., Chen Y., Wang J., Huang W., Meng H., SmartMat, 2023, 4, e1153.
[6] Li J., Shen P., Zhao Z., Tang B. Z., CCS Chemistry, 2019, 181.
[7] Ding Y., Zhao Y., Liu Y., Aggregate, 2024, 5, e626.
[8] Wöhler F., Abhandlungen der Königlichen Gesellschaft der Wissenschaften in Göttingen, 1845, 2, 225.
[9] Stahly G. P., Crystal Growth & Design, 2009, 9, 4212.
[10] Aitipamula S., Banerjee R., Bansal A. K., Biradha K., Cheney M. L., Choudhury A. R., Desiraju G. R., Dikundwar A. G., Dubey R., Duggirala N., Ghogale P. P., Ghosh S., Goswami P. K., Goud N. R., Jetti R. R. K. R., Karpinski P., Kaushik P., Kumar D., Kumar V., Moulton B., Mukherjee A., Mukherjee G., Myerson A. S., Puri V., Ramanan A., Rajamannar T., Reddy C. M., Rodriguez-Hornedo N., Rogers R. D., Row T. N. G., Sanphui P., Shan N., Shete G., Singh A., Sun C. C., Swift J. A., Thaimattam R., Thakur T. S., Kumar Thaper R., Thomas S. P., Tothadi S., Vangala V. R., Variankaval N., Vishweshwar P., Weyna D. R., Zaworotko M. J., Crystal Growth & Design, 2012, 12, 2147.
[11] Coleman L., Cohen M., Sandman D. J., Yamagishi F., Garito A. F., Heeger A., Solid State Communications, 1973, 12, 1125.
[12] Mathur C., Gupta R., Bansal R. K., Chemistry—A European Journal, 2024, 30, e202304139.
[13] Sun Y.-Q., Lei Y.-L., Sun X.-H., Lee S.-T., Liao L.-S., Chemistry of Materials, 2015, 27, 1157.
[14] Huang Q., Ye X., Chen W., Song X., Chen Y.-t., Wen X., Zhang M., Wang Y., Chen S.-L., Dang L., Li M.-D., ACS Energy Letters, 2023, 8, 4179.
[15] Jiang Q., Zhang J., Mao Z., Yao Y., Zhao D., Jia Y., Hu D., Ma Y., Advanced Materials, 2022, 34, e2108103.
[16] Ou C., Na W., Ge W., Huang H., Gao F., Zhong L., Zhao Y., Dong X., Angewandte Chemie International Edition, 2021, 60, 7985.
[17] Zhou B., Zhao Q., Tang L., Yan D., Chemical Communications, 2020, 56, 7698.
[18] Liu C. H., Niazi M. R., Perepichka D. F., Angewandte Chemie International Edition, 2019, 58, 17312.
[19] Bolla G., Dong H., Zhen Y., Wang Z., Hu W., Science China Materials, 2016, 59, 523.
[20] Kagawa F., Horiuchi S., Tokunaga M., Fujioka J., Tokura Y., Nature Physics, 2010, 6, 169.
[21] Zhu W., Dong H., Zhen Y., Hu W., Science China Materials, 2015, 58, 854.
[22] Sato R., Kawamoto T., Mori T., Journal of Materials Chemistry C, 2019, 7, 567.
[23] Andersson K., Theoretical Chemistry Accounts, 2023, 142, 58.
[24] Vo N. T., Bond A. M., Martin L. L., Inorganica Chimica Acta, 2020, 505, 119458.
[25] Ding X., Wei C., Wang L., Yang J., Huang W., Chang Y., Ou C., Lin J., Huang W., SmartMat, 2024, 5, e1213.
[26] Zhang J., Xu W., Sheng P., Zhao G., Zhu D., Accounts of Chemical Research, 2017, 50, 1654.
[27] Coropceanu V., Cornil J., da Silva Filho D. A., Olivier Y., Silbey R., Brédas J.-L., Chemical Reviews, 2007, 107, 926.
[28] Saha S., Desiraju G. R., The Journal of American Chemical Society, 2018, 140, 6361.
[29] Mahns B., Kataeva O., Islamov D., Hampel S., Steckel F., Hess C., Knupfer M., Büchner B., Himcinschi C., Hahn T., Renger R., Kortus J., Crystal Growth & Design, 2014, 14, 1338.
[30] Zhang H., Guo C., Wang X., Xu J., He X., Liu Y., Liu X., Huang H., Sun J., Crystal Growth & Design, 2013, 13, 679.
[31] Portalone G., Rissanen K., Crystal Growth & Design, 2018, 18, 5904.
[32] Zhang P., Bolla G., Qiu G., Shu Z., Yan Q., Li Q., Ding S., Ni Z., Zhu W., Dong H., Zhen Y., Hu W., CrystEngComm, 2017, 19, 4505.
[33] Zhuo M. P., Yuan Y., Su Y., Chen S., Chen Y. T., Feng Z. Q., Qu Y. K., Li M. D., Li Y., Hu B. W., Wang X. D., Liao L. S., Advanced Materials, 2022, 34, 2107169.
[34] Hu P., Du K., Wei F., Jiang H., Kloc C., Crystal Growth & Design, 2016, 16, 3019.
[35] Wu B., Zhuo M. P., Chen S., Su Y., Yu Y. J., Fan J. Z., Wang Z. S., Wang X. D., Advanced Optical Materials, 2023, 11, 2202895.
[36] Dar A. A., Rashid S., CrystEngComm, 2021, 23, 8007.
[37] Joo B., Kim E. G., Physical Chemistry Chemical Physics, 2016, 18, 17890.
[38] Kistenmacher T., Emge T., Wiygul F., Bryden W., Chappell J., Stokes J., Chiang L., Cowan D., Bloch A., Solid State Communications, 1981, 39, 415.
[39] Usman R., Khan A., Sun H., Wang M., Journal of Solid State Chemistry, 2018, 266, 112.
[40] Fang X., Yang X., Li D., Lu B., Yan D., Crystal Growth & Design, 2018, 18, 6470.
[41] Wei Q., Liu L., Xiong S., Zhang X., Deng W., Zhang X., Jie J., Journal of Physical Chemistry Letters, 2020, 11, 359.
[42] Sakai M., Sakuma H., Ito Y., Saito A., Nakamura M., Kudo K., Physical Review B, 2007, 76, 045111.
[43] Goetz K. P., Tsutsumi J., Pookpanratana S., Chen J., Corbin N. S., Behera R. K., Coropceanu V., Richter C. A., Hacker C. A., Hasegawa T., Jurchescu O. D., Advanced Electronic Materials, 2016, 2, 1600203.
[44] Liu X.-X., Shi P., Dai X.-L., Huang Y.-L., Lu T.-B., Chen J.-M., CrystEngComm, 2022, 24, 8449.
[45] Mandal A., CrystEngComm, 2022, 24, 6579.
[46] Mandal A., Choudhury A., Sau S., Iyer P. K., Mal P., The Journal of Physical Chemistry C, 2020, 124, 6544.
[47] Li T., Melis S., Bagade C., Khatib A., Kosarzycki R., Maglieri G., Zhang X., Van Keuren E., Journal of Nanoparticle Research, 2019, 21, 47.
[48] Acker D. S., Hertler W. R., Journal of the American Chemical Society, 1962, 84, 3370.
[49] Wang W., Luo L., Sheng P., Zhang J., Zhang Q., Chemistry—A European Journal, 2021, 27, 464.
[50] Shi P., Liu X.-X., Dai X.-L., Lu T.-B., Chen J.-M., CrystEngComm, 2022, 24, 4622.
[51] Kadoya T., de Caro D., Jacob K., Faulmann C., Valade L., Mori T., Journal of Materials Chemistry, 2011, 21, 18421.
[52] Ji L. F., Fan J. X., Zhang S. F., Ren A. M., Physical Chemistry Chemical Physics, 2018, 20, 3784.
[53] Huang Y., Ning L., Zhang X., Zhou Q., Gong Q., Zhang Q., Chemical Society Reviews, 2024, 53, 1090.
[54] Ferraris J., Cowan D., Walatka V., Perlstein J. H., Journal of the American Chemical Society, 1973, 95, 948.
[55] Kunkeler P. J., van Koningsbruggen P. J., Cornelissen J. P., van der Horst A. N., van der Kraan A. M., Spek A. L., Haasnoot J. G., Reedijk J., Journal of the American Chemical Society, 1996, 118, 2190.
[56] Jérome D., Schulz H. J., Advances in Physics, 2006, 31, 299.
[57] Shokaryev I., Buurma A., Jurchescu O., Uijttewaal M. A., De Wijs G., Palstra M. T. T., de Groot R. A., The Journal of Physical Chemistry A, 2008, 112, 2497.
[58] Bond A. M., Fletcher S., Marken F., Shaw S. J., Symons P. G., Journal of the Chemical Society, Faraday Transactions, 1996, 92, 3925.
[59] Shukla R., Ruzie C., Schweicher G., Kennedy A. R., Geerts Y. H., Chopra D., Chattopadhyay B., Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials, 2019, 75, 71.
[60] Chernyshov I. Y., Vener M. V., Feldman E. V., Paraschuk D. Y., Sosorev A. Y., Journal of Physical Chemistry Letters, 2017, 8, 2875.
[61] Umar Y., Parlak C., Haque S. K. M., Appu S. P., Ashwaq O., Ramasami P., Journal of the Indian Chemical Society, 2021, 98, 100032.
[62] Wang X., Wang Z., Wang X., Kang F., Gu Q., Zhang Q., Angewandte Chemie International Edition, 2024, 136, e202416181.
[63] Tang B., Li W. L., Chang Y., Yuan B., Wu Y., Zhang M. T., Xu J. F., Li J., Zhang X., Angewandte Chemie International Edition, 2019, 58, 15526.
[64] Zhu W., Yi Y., Zhen Y., Hu W., Small, 2015, 11, 2150.
[65] Chu M., Qiu B., Zhang W., Zhou Z., Yang X., Yan Y., Yao J., Li Y. J., Zhao Y. S., ACS Applied Materials & Interfaces, 2018, 10, 42740.
[66] Zhu W., Zhen Y., Dong H., Fu H., Hu W., Progress in Chemistry, 2014, 26, 1292.
[67] Rodríguez-Fernández J., Robledo M., Lauwaet K., Martín-Jiménez A., Cirera B., Calleja F., Díaz-Tendero S., Alcamí M., Floreano L., Domínguez-Rivera M., Vázquez de Parga A. L., Écija D., Gallego J. M., Miranda R., Martín F., Otero R., The Journal of Physical Chemistry C, 2017, 121, 23505.
[68] Moayedpour S., Bier I., Wen W., Dardzinski D., Isayev O., Marom N., The Journal of Physical Chemistry C, 2023, 127, 10398.
[69] Van Geijn E., Wang K., de Jong M. P., Journal of Chemical Physics, 2016, 144, 174708.
[70] Chen Z., Lu X., Qiao J., Liu J., Qin W., Nano Letters, 2022, 22, 5481.
[71] Ding Z., Mu Q., Ren J., Li Y., Shen Q., Zhang L., Zhang S., Journal of Physics: Conference Series, 2023, 2610, 012054.
[72] Ou C., Na W., Ge W., Huang H., Gao F., Zhong L., Zhao Y., Dong X., Angewandte Chemie, 2021, 133, 8238.
[73] Wang D., Kan X., Wu C., Gong Y., Guo G., Liang T., Wang L., Li Z., Zhao Y., Chemical Communication, 2020, 56, 5223.
[74] Zhu W., Zhu L., Zou Y., Wu Y., Zhen Y., Dong H., Fu H., Wei Z., Shi Q., Hu W., Advanced Materials, 2016, 28, 5954.
[75] Ai Q., Getmanenko Y. A., Jarolimek K., Castaneda R., Timofeeva T. V., Risko C., J Phys Chem Lett, 2017, 8, 4510.
[76] Guo J., Xu L., Cai M., Dong Z., Mu Q., Wang X., Fan H., Teng F., He X., Jiang H., Hu P., Crystal Growth & Design, 2024, 24, 1293.
[77] Dobrowolski M. A., Garbarino G., Mezouar M., Ciesielski A., Cyrański M. K., CrystEngComm, 2014, 16, 415.
[78] Mandal A., Swain P., Nath B., Sau S., Mal P., CrystEngComm, 2019, 21, 981.
[79] Wen X., Shao Y., Chen Y. T., He J., Chen S. L., Dang L., Li M. D., RSC Advances, 2024, 14, 4503.
[80] Wu H. D., Wang F. X., Zhang M., Pan G. B., Nanoscale, 2015, 7, 12839.
[81] Zhang J., Liu G., Zhou Y., Long G., Gu P., Zhang Q., ACS Applied Materials & Interfaces, 2017, 9, 1183.
[82] Xie Z., Hu B. L., Li R. W., Zhang Q., ACS Omega, 2021, 6, 9319.
[83] Arunan E., Desiraju G. R., Klein R. A., Sadlej J., Scheiner S., Alkorta I., Clary D. C., Crabtree R. H., Dannenberg J. J., Hobza P., Kjaergaard H. G., Legon A. C., Mennucci B., Nesbitt D. J., Pure and Applied Chemistry, 2011, 83, 1619.
[84] Jiang M., Li S., Zhen C., Wang L., Li F., Zhang Y., Dong W., Zhang X., Hu W., Frontiers of Optoelectronics, 2022, 15, 21.
[85] Higashino T., Dogishi M., Kadoya T., Sato R., Kawamoto T., Mori T., Journal of Materials Chemistry C, 2016, 4, 5981.
[86] Wu X., Wang M., Du M., Lu J., Chen J., Khan A., Usman R., Wei X., Feng Q., Xu C., Crystal Growth & Design, 2014, 15, 434.
[87] Sun H., Wang M., Wei X., Zhang R., Wang S., Khan A., Usman R., Feng Q., Du M., Yu F., Zhang W., Xu C., Crystal Growth & Design, 2015, 15, 4032.
[88] Khan A., Wang M., Usman R., Lu J., Sun H., Du M., Zhang R., Xu C., New Journal of Chemistry, 2016, 40, 5277.
[89] Sun L., Zhu W., Zhang X., Li L., Dong H., Hu W., Journal of the American Chemical Society, 2021, 143, 19243.
[90] Mandal A., Rissanen K., Mal P., CrystEngComm, 2019, 21, 4401.
[91] Pang X., Wang H., Wang W., Jin W. J., Crystal Growth & Design, 2015, 15, 4938.
[92] Goud N. R., Matzger A. J., Crystal Growth & Design, 2016, 17, 328.
[93] Wang Z., Yu F., Chen W., Wang J., Liu J., Yao C., Zhao J., Dong H., Hu W., Zhang Q., Angewandte Chemie International Edition, 2020, 59, 17580.
[94] Takahashi Y., Hasegawa T., Abe Y., Tokura Y., Nishimura K., Saito G., Applied Physics Letters, 2005, 86, 063504.
[95] Mandal A., Mohn C. E., Görbitz C. H., Rogowska M., Nilsen O., Molecular Systems Design & Engineering, 2025, 10, 519.
[96] Wu H.-D., Wang F.-X., Xiao Y., Pan G.-B., Journal of Materials Chemistry C, 2014, 2, 2328.
[97] Vermeulen D., Zhu L. Y., Goetz K. P., Hu P., Jiang H., Day C. S., Jurchescu O. D., Coropceanu V., Kloc C., McNeil L. E., The Journal of Physical Chemistry C, 2014, 118, 24688.
[98] Mezzadri F., Castagnetti N., Masino M., Girlando A., Crystal Growth & Design, 2018, 18, 5592.
[99] Feng Q., Wang M., Dong B., Xu C., Zhao J., Zhang H., CrystEngComm, 2013, 15, 3623.