ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Figure 1Loading Img

Crystal Structures, Reaction Rates, and Selected Physical Properties of Halo-Boronsubphthalocyanines (Halo = Fluoride, Chloride, and Bromide)

View Author Information
Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, Ontario, Canada M5S 3E5
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada, M5S 3H6
§ Department of Materials Science and Engineering, University of Toronto, 184 College Street, Toronto, Ontario, Canada M5S 3E4
Cite this: J. Chem. Eng. Data 2012, 57, 10, 2756–2765
Publication Date (Web):August 27, 2012
Copyright © 2012 American Chemical Society

    Article Views





    Other access options
    Supporting Info (3)»


    Abstract Image

    The physical properties, including the solid state arrangement, photophysics, solubility, and electrochemical behavior of a series of halo-BsubPcs (halo = F, Cl, Br) have been measured (IUPAC name halo-(7,12:14,19-diimino-21,5-nitrilo-5H-tribenzo(c,h,m)(1,6,11)triazacyclopentadecinato)-boron(III)). We have found that across the series all are relatively similar in most regards. Exceptions include that F-BsubPc can be 5 to 25 times more soluble than Cl-BsubPc in common organic solvents. F-BsubPc was also found to be hydrolytically stable under the conditions tested, whereas Cl-BsubPc and Br-BsubPc readily hydrolyzed to form HO-BsubPc. The relative rates of reaction for the series of halo-BsubPcs under standard phenoxylation conditions have also been measured. It was found that F-BsubPc does not undergo phenoxylation, whereas Br-BsubPc showed a markedly higher reaction rate relative to Cl-BsubPc. Based on these data some assumptions can be made as to the suitability of either F-BsubPc or Br-BsubPc to be used in place of the more common Cl-BsubPc. The data indicate that F-BsubPc is a potential replacement for Cl-BsubPc in organic electronic materials whereas Br-BsubPc might be more suitable as a chemical intermediate. Comments on the synthetic methods used to produce each halo-BsubPc are also made.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.


    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    Jump To

    Thermal ellipsoid plots, standard crystallographic tables, and a table of molar and specific solubilities. This material is available free of charge via the Internet at

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 61 publications.

    1. Adam R. Tetreault, Itzel Lopez-Carreon, Marzieh Riahnezhad, Elnaz Esmizadeh, Peter Collins, Kamran Alasvand Zarasvand, Naren Vivekanandan, Ajinkya Mandlik, Michelle Fernandes, Kevin Golovin, Timothy P. Bender. Assessing Individual Material Degradation toward Organic Solar Cells Using Accelerated Nanolayer Lifetime Protocols: Implications for Solar Cell Longevity. ACS Applied Nano Materials 2024, 7 (4) , 4182-4198.
    2. Benjamin J. Knapik, Rachel Zigelstein, Marko Saban, Timothy P. Bender. Reaction Calorimetry and Scale-Up Considerations of Bromo- and Chloro-Boron Subphthalocyanine. ACS Chemical Health & Safety 2023, 30 (5) , 287-301.
    3. Nina F. Farac, Adam R. Tetreault, Timothy P. Bender. Cs-Symmetric, Peripherally Fluorinated Boron Subphthalocyanine–Subnaphthalocyanine Hybrids: Shedding New Light on Their Fundamental Photophysical Properties and Their Functionality as Optoelectronic Materials. The Journal of Physical Chemistry C 2023, 127 (1) , 702-727.
    4. Devon P. Holst, Pascal Friederich, Alán Aspuru-Guzik, Timothy P. Bender. Updated Calibrated Model for the Prediction of Molecular Frontier Orbital Energies and Its Application to Boron Subphthalocyanines. Journal of Chemical Information and Modeling 2022, 62 (4) , 829-840.
    5. Kathleen L. Sampson, Stephanie R. Nyikos, Graham E. Morse, Timothy P. Bender. Sequentially Solution-Deposited Active Layer: Ideal Organic Photovoltaic Device Architecture for Boron Subphthalocyanine as a Nonfullerene Acceptor. ACS Applied Energy Materials 2021, 4 (2) , 1237-1249.
    6. Hasan Raboui, David S. Josey, Yin Jin, Timothy P. Bender. Initial Engineering and Outdoor Stability Assessment of “Gray/Black” Fullerene-Free Organic Photovoltaics Based on Only Two Complementary Absorbing Materials: A Tetrabenzotriazacorrole and a Subphthalocyanine. ACS Omega 2020, 5 (39) , 25264-25272.
    7. Amir Mizrahi, Esmeralda Bukuroshi, Jenya Vestfrid, Timothy P. Bender, Zeev Gross. Axial/Peripheral Chloride/Fluoride-Substituted Boron Subphthalocyanines as Electron Acceptors. Inorganic Chemistry 2020, 59 (5) , 2641-2645.
    8. Esmeralda Caballero, David Guzmán, Tomás Torres, M. Salomé Rodríguez-Morgade. Expanding the Subporphyrazine Chromophore by Conjugation of Phenylene and Vinylene Substituents: Rainbow SubPzs. The Journal of Organic Chemistry 2020, 85 (4) , 1948-1960.
    9. Giovanni Bressan, Andrew N. Cammidge, Garth A. Jones, Ismael A. Heisler, Daniel Gonzalez-Lucas, Sonia Remiro-Buenamañana, Stephen R. Meech. Electronic Energy Transfer in a Subphthalocyanine–Zn Porphyrin Dimer Studied by Linear and Nonlinear Ultrafast Spectroscopy. The Journal of Physical Chemistry A 2019, 123 (27) , 5724-5733.
    10. Trevor M. Grant, Victoria McIntyre, Jenya Vestfrid, Hasan Raboui, Robin T. White, Zheng-Hong Lu, Benoît H. Lessard, Timothy P. Bender. Straightforward and Relatively Safe Process for the Fluoride Exchange of Trivalent and Tetravalent Group 13 and 14 Phthalocyanines. ACS Omega 2019, 4 (3) , 5317-5326.
    11. David S. Josey, Grayson L. Ingram, Richard K. Garner, Jonathan M. Wang, Greg J. Evans, Zheng-Hong Lu, Timothy P. Bender. Outdoor Stability of Chloro–(Chloro)n–Boron Subnaphthalocyanine and Chloro–Boron Subphthalocyanine as Electron Acceptors in Bilayer and Trilayer Organic Photovoltaics. ACS Applied Energy Materials 2019, 2 (2) , 979-986.
    12. Kathleen L. Sampson, Xiaoqin Jiang, Esmeralda Bukuroshi, Aleksa Dovijarski, Hasan Raboui, Timothy P. Bender, Karl M. Kadish. A Comprehensive Scope of Peripheral and Axial Substituent Effect on the Spectroelectrochemistry of Boron Subphthalocyanines. The Journal of Physical Chemistry A 2018, 122 (18) , 4414-4424.
    13. Kathleen L. Sampson, David S. Josey, Yiying Li, Jessica D. Virdo, Zheng-Hong Lu, and Timothy P. Bender . Ability To Fine-Tune the Electronic Properties and Open-Circuit Voltage of Phenoxy-Boron Subphthalocyanines through Meta-Fluorination of the Axial Substituent. The Journal of Physical Chemistry C 2018, 122 (2) , 1091-1102.
    14. Zikuan Wang and Xuefeng Fu . Synthesis, Characterization, and Reactivity Studies of Subphthalocyanine Boron Triflate. Organometallics 2017, 36 (2) , 285-290.
    15. Julia Guilleme, Lara Martínez-Fernández, David González-Rodríguez, Inés Corral, Manuel Yáñez, and Tomás Torres . An Insight into the Mechanism of the Axial Ligand Exchange Reaction in Boron Subphthalocyanine Macrocycles. Journal of the American Chemical Society 2014, 136 (40) , 14289-14298.
    16. Nicola Beaumont, Jeffrey S. Castrucci, Paul Sullivan, Graham E. Morse, Andrew S. Paton, Zheng-Hong Lu, Timothy P. Bender, and Tim S. Jones . Acceptor Properties of Boron Subphthalocyanines in Fullerene Free Photovoltaics. The Journal of Physical Chemistry C 2014, 118 (27) , 14813-14823.
    17. Kwang-Hee Lee, Gae Hwang Lee, Dong-Seok Leem, Jiyoul Lee, Jong Won Chung, Xavier Bulliard, Hyeonho Choi, Kyung-Bae Park, Kyu-Sik Kim, Yong Wan Jin, Sangyoon Lee, and Soo Young Park . Dynamic Characterization of Green-Sensitive Organic Photodetectors Using Nonfullerene Small Molecules: Frequency Response Based on the Molecular Structure. The Journal of Physical Chemistry C 2014, 118 (25) , 13424-13431.
    18. Graham E. Morse, Ivan Gong, Yazan Kawar, Alan J. Lough, and Timothy P. Bender . Crystal and Solid-State Arrangement Trends of Halogenated Boron Subphthalocyanines. Crystal Growth & Design 2014, 14 (5) , 2138-2147.
    19. Christian G. Claessens, David González-Rodríguez, M. Salomé Rodríguez-Morgade, Anaïs Medina, and Tomás Torres . Subphthalocyanines, Subporphyrazines, and Subporphyrins: Singular Nonplanar Aromatic Systems. Chemical Reviews 2014, 114 (4) , 2192-2277.
    20. Andrew S. Paton, Graham E. Morse, Alan J. Lough, and Timothy P. Bender . Utilizing the π-Acidity of Boron Subphthalocyanine To Achieve Novel Solid-State Arrangements. Crystal Growth & Design 2013, 13 (12) , 5368-5374.
    21. Devon P. Holst, Aleksa Dovijarski, Alan J. Lough, Timothy P. Bender. Triphenyl borates used to avoid the bay-position halogenation of boron subnaphthalocyanines; and for the subnaphthalocyanine, subphthalocyanine and hybrids formation. New Journal of Chemistry 2024, 4
    22. Serguei M. Arabei, Piotr P. Pershukevich, Mikhail V. Belkov, Lev L. Gladkov, Anastasiya A. Tabolich, Konstantin N. Solovyov, Ivan A. Skvortsov, Pavel A. Stuzhin. Phosphorescence of hexachlorosubstituted subphthalocyanine and its pyrazine analogue. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2023, 302 , 123052.
    23. Giulia Lavarda, Jorge Labella, M. Victoria Martínez-Díaz, M. Salomé Rodríguez-Morgade, Atsuhiro Osuka, Tomás Torres. Recent advances in subphthalocyanines and related subporphyrinoids. Chemical Society Reviews 2022, 51 (23) , 9482-9619.
    24. Ivan D. Burtsev, Tatiana V. Dubinina, Anton E. Egorov, Alexey A. Kostyukov, Anna V. Shibaeva, Alina S. Agranat, Maria M. Ivanova, Lev R. Sizov, Natalia V. Filatova, Alexander Y. Rybkin, Elena V. Varakina, Alexander S. Bunev, Anastasia A. Antonets, Elena R. Milaeva, Vladimir A. Kuzmin. Substituted boron subphthalocyanines – Prospective compounds for theranostics: Synthesis, photochemical properties and in vitro cytotoxicity. Dyes and Pigments 2022, 207 , 110690.
    25. Mariana Hildebrand, Devon Holst, Timothy Bender, Leeor Kronik. Electronic Structure, Bonding, and Stability of Boron Subphthalocyanine Halides and Pseudohalides. Advanced Theory and Simulations 2022, 5 (4)
    26. Matthias Lehmann, Maximilian Baumann, Martin Lambov, Alexey Eremin. Parallel Polar Dimers in the Columnar Self‐Assembly of Umbrella‐Shaped Subphthalocyanine Mesogens. Advanced Functional Materials 2021, 31 (38)
    27. Esmeralda Bukuroshi, Siena Wong, Thanmayee Mudigonda, Kyle Nova, Antoine Dumont, Devon Holst, Zheng-Hong Lu, Timothy P. Bender. Molecular engineering of α and β peripherally tri-halogenated substituted boron subphthalocyanines as mixed alloys to control physical and electrochemical properties for organic photovoltaic applications. Molecular Systems Design & Engineering 2021, 6 (4) , 308-326.
    28. Jorge Labella, Elisa López-Serrano, Tomás Torres. Boosting the Stability of Boron Peroxides through Subphthalocyanine Coordination. Organic Materials 2021, 03 (02) , 141-145.
    29. Cheng Zhang, Yuan Guo, Dan He, Jouji Komiya, Go Watanabe, Takuya Ogaki, Chengyuan Wang, Atsuko Nihonyanagi, Hiroyuki Inuzuka, Hao Gong, Yuanping Yi, Kazuo Takimiya, Daisuke Hashizume, Daigo Miyajima. A Design Principle for Polar Assemblies with C 3 ‐Sym Bowl‐Shaped π‐Conjugated Molecules. Angewandte Chemie 2021, 133 (6) , 3298-3304.
    30. Cheng Zhang, Yuan Guo, Dan He, Jouji Komiya, Go Watanabe, Takuya Ogaki, Chengyuan Wang, Atsuko Nihonyanagi, Hiroyuki Inuzuka, Hao Gong, Yuanping Yi, Kazuo Takimiya, Daisuke Hashizume, Daigo Miyajima. A Design Principle for Polar Assemblies with C 3 ‐Sym Bowl‐Shaped π‐Conjugated Molecules. Angewandte Chemie International Edition 2021, 60 (6) , 3261-3267.
    31. Mathias Dowds, Mogens Brøndsted Nielsen. Controlling the optical properties of boron subphthalocyanines and their analogues. Molecular Systems Design & Engineering 2021, 6 (1) , 6-24.
    32. Yasuhiro Kubota. BODIPY Dyes and Their Analogues. 2021, 119-220.
    33. Mads Georg Rasmussen, Henrik Gotfredsen, Anders Kadziola, Mogens Brøndsted Nielsen. Towards novel thieno-fused subporphyrazines via functionalized thiophene precursors. Journal of Sulfur Chemistry 2020, 41 (4) , 357-368.
    34. Pieter J. Swarts, Jeanet Conradie. Oxidation and reduction data of subphthalocyanines. Data in Brief 2020, 28 , 105039.
    35. Pieter J. Swarts, Jeanet Conradie. Electrochemical behaviour of chloro- and hydroxy- subphthalocyanines. Electrochimica Acta 2020, 329 , 135165.
    36. Guo Li, Shaohui Zheng. A computational study of the effects of axial halogen substitutions of boron subphthalocyanines on their electronic spectra in solution and in the solid state. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2019, 222 , 117180.
    37. Esmeralda Bukuroshi, Jenya Vestfrid, Zeev Gross, Timothy P. Bender. Fluorinated boron subphthalocyanines: Lewis acid based templating chemistry facilitates random halide exchange, and fluoride versus chloride affects the basic photophysical properties and the solid-state arrangement. New Journal of Chemistry 2019, 43 (42) , 16730-16737.
    38. Guo Li, Shaohui Zheng. Exploring the effects of axial halogen substitutions of boron subphthalocyanines on the performance of BsubPC/C60 organic solar cells: a DFT/TDDFT-based computational study. New Journal of Chemistry 2019, 43 (32) , 12719-12726.
    39. Michael J. Waters, Daniel Hashemi, Guangsha Shi, Emmanouil Kioupakis, John Kieffer. Predictive Simulations for Tuning Electronic and Optical Properties of SubPc Derivatives. Journal of Electronic Materials 2019, 48 (5) , 2962-2970.
    40. Pavel A. Stuzhin, Ivan A. Skvortsov, Yuriy A. Zhabanov, Nikolai V. Somov, Oleg V. Razgonyaev, Ivan A. Nikitin, Oskar I. Koifman. Subphthalocyanine azaanalogues – Boron(III) subporphyrazines with fused pyrazine fragments. Dyes and Pigments 2019, 162 , 888-897.
    41. Seongwon Yoon, Kyu Min Sim, Dae Sung Chung. Prospects of colour selective organic photodiodes. Journal of Materials Chemistry C 2018, 6 (48) , 13084-13100.
    42. Xue Chen, Shaohui Zheng. Inferring the molecular arrangements of boron subphthalocyanine chloride in thin film from a DFT/TDDFT study of molecular clusters and experimental electronic absorption spectra. Organic Electronics 2018, 62 , 667-675.
    43. Germán Zango, Tsuneaki Sakurai, Beatriz Urones, Hidenori Saeki, Wakana Matsuda, M. Victoria Martínez‐Díaz, Shu Seki, Tomás Torres. Peripherally Cyanated Subphthalocyanines as Potential n‐Type Organic Semiconductors. Chemistry – A European Journal 2018, 24 (33) , 8331-8342.
    44. Dongye Xing, Yanjun Hou, Haijun Niu. Synthesis and fluorescence properties of some difluoroboron β-diketonate complexes and composite containing PMMA. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2018, 193 , 71-77.
    45. Leart Sejdarasi, Katherine J. McAuliffe, Brooke A. Corbin, Evan R. Trivedi. Synthesis and Characterization of Mixed Fluorinated Phenylthio‐ Subphthalocyanines. ChemistrySelect 2017, 2 (24) , 7417-7420.
    46. Katherine McAuliffe, Megan Kaster, Regina Szlag, Evan Trivedi. Low-Symmetry Mixed Fluorinated Subphthalocyanines as Fluorescence Imaging Probes in MDA-MB-231 Breast Tumor Cells. International Journal of Molecular Sciences 2017, 18 (6) , 1177.
    47. Kyounghoon Lee, Courtney M. Donahue, Scott R. Daly. Triaminoborane-bridged diphosphine complexes with Ni and Pd: coordination chemistry, structures, and ligand-centered reactivity. Dalton Transactions 2017, 46 (29) , 9394-9406.
    48. Akuto Takagi, Tadashi Mizutani. Control of the molecular packing of chloroboron( iii ) and fluoroboron( iii ) subnaphthalocyanines by designing peripheral substituents. RSC Advances 2017, 7 (85) , 54235-54245.
    49. Koji Yamamoto, Akuto Takagi, Miyako Hada, Ryosuke Taniwaki, Tadashi Mizutani, Yoshifumi Kimura, Yuko Takao, Kazuyuki Moriwaki, Fukashi Matsumoto, Takatoshi Ito, Toshiyuki Iwai, Koichi Hida, Takumi Mizuno, Toshinobu Ohno. Synthesis and optoelectronic properties of hexachloro- and hexaiodosubnaphthalocyanines as organic electronic materials. Tetrahedron 2016, 72 (32) , 4918-4924.
    50. Tatiana V. Dubinina, Marina M. Osipova, Anton V. Zasedatelev, Vitaly I. Krasovskii, Nataliya E. Borisova, Stanislav A. Trashin, Larisa G. Tomilova, Nikolay S. Zefirov. Synthesis, optical and electrochemical properties of novel phenyl- and phenoxy-substituted subphthalocyanines. Dyes and Pigments 2016, 128 , 141-148.
    51. Trevor Plint, Benoît H. Lessard, Timothy P. Bender. Assessing the potential of group 13 and 14 metal/metalloid phthalocyanines as hole transport layers in organic light emitting diodes. Journal of Applied Physics 2016, 119 (14)
    52. Jessica D. Virdo, Alan J. Lough, Timothy P. Bender. Redetermination of the crystal structure of boron subphthalocyanine chloride (Cl-BsubPc) enabled by slow train sublimation. Acta Crystallographica Section C Structural Chemistry 2016, 72 (4) , 297-307.
    53. Catherine Bonnier, Timothy Bender. Ring Opening Reactions through C-O Bond Cleavage Uniquely Adding Chemical Functionality to Boron Subphthalocyanine. Molecules 2015, 20 (10) , 18237-18245.
    54. David S. Josey, Jeffrey S. Castrucci, Jeremy D. Dang, Benoît H. Lessard, Timothy P. Bender. Evaluating Thiophene Electron‐Donor Layers for the Rapid Assessment of Boron Subphthalocyanines as Electron Acceptors in Organic Photovoltaics: Solution or Vacuum Deposition?. ChemPhysChem 2015, 16 (6) , 1245-1250.
    55. Norihito Iida, Etsuko Tokunaga, Norimichi Saito, Norio Shibata. Pentafluorosulfanyl (SF5) in dyes: C3-Regioselective synthesis of α-mono-substituted subphthalocyanine with SF5-phenyl group. Journal of Fluorine Chemistry 2015, 171 , 120-123.
    56. Jeremy D. Dang, Mabel V. Fulford, Brett A. Kamino, Andrew S. Paton, Timothy P. Bender. Process for the synthesis of symmetric and unsymmetric oxygen bridged dimers of boron subphthalocyanines (μ-oxo-(BsubPc) 2 s). Dalton Transactions 2015, 44 (9) , 4280-4288.
    57. Benoît H. Lessard, Mohammad AL-Amar, Trevor M. Grant, Robin White, Zheng-Hong Lu, Timothy P. Bender. From chloro to fluoro, expanding the role of aluminum phthalocyanine in organic photovoltaic devices. Journal of Materials Chemistry A 2015, 3 (9) , 5047-5053.
    58. Hasan Raboui, Mohammad AL-Amar, Ahmed I. Abdelrahman, Timothy P. Bender. Axially phenoxylated aluminum phthalocyanines and their application in organic photovoltaic cells. RSC Advances 2015, 5 (57) , 45731-45739.
    59. Catherine Bonnier, David S. Josey, Timothy P. Bender. Aryl-Substituted Boron Subphthalocyanines and their Application in Organic Photovoltaics. Australian Journal of Chemistry 2015, 68 (11) , 1750.
    60. Benoît H. Lessard, Timothy P. Bender, . Controlled and selective placement of boron subphthalocyanines on either chain end of polymers synthesized by nitroxide mediated polymerization. AIMS Molecular Science 2015, 2 (4) , 411-426.
    61. Andrew S. Paton, Timothy P. Bender. Some observations regarding the behavior of boron subphthalocyanines in polar aprotic solvents. Journal of Porphyrins and Phthalocyanines 2014, 18 (10n11) , 1051-1056.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect