The influence of metal cations on the formation of phthalocyanine/porphyrin heterodimers and nanoporous cocrystals

Shannah Kerrigan; Nikolaos Angelos Stamos; Alexander Stiven; Emma Johnson; Benjamin Plevey; Catherine Newman; Gary S. Nichol; Neil B. Mckeown

doi:10.1142/S1088424625501111

The influence of metal cations on the formation of phthalocyanine/porphyrin heterodimers and nanoporous cocrystals

Shannah Kerrigan, Nikolaos Angelos Stamos, Alexander Stiven, Emma Johnson, Benjamin Plevey, Catherine Newman, Gary S. Nichol, Neil B. Mckeown^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

Porphyrin-containing Phthalocyanine Nanoporous Crystals (PNCs) have been prepared previously by the cocrystallisation of octa(2′,6′-di-iso-propyphenoxy)phthalocyanine [(dipPhO)₈Pc] and its metalated derivatives with metal-free tetraphenylporphyrin (TPP). Here we report the effect of the central cations (M = H₂, Co, Cu, Zn) on heterodimer formation, both in solution and in cocrystallisations, for all sixteen possible combinations of (dipPhO)₈PcM with TPPM. UV/visible spectroscopy shows a clear trend of Cu²⁺ > 2H⁺ > Co²⁺ > Zn²⁺ for encouraging or discouraging heterodimer formation, which can be rationalised by the propensity of the metal cation to bind to axial ligands when incorporated into porphyrin or phthalocyanine macrocycles. Attempted cocrystallisations of all 16 (dipPhO)₈PcM/TPPM combinations yielded 13 heterodimer-based PNCs, with only (dipPhO)₈PcZn failing to provide a cocrystal with TPPM (Co, Cu, Zn). This study further demonstrates the remarkable efficiency of (dipPhO)₈PcM in directing the structure of PNC cocrystallisations. It suggests a simple method for placing two metal cations of choice within van der Waals distance of one another within a well-defined, predictable crystal structure.

Original language	English
Journal	Journal of porphyrins and phthalocyanines
Early online date	2 Dec 2025
DOIs	https://doi.org/10.1142/S1088424625501111
Publication status	E-pub ahead of print - 2 Dec 2025

Keywords / Materials (for Non-textual outputs)

crystal
heterodimer
phthalocyanine
tetraphenylporphyrin

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10.1142/S1088424625501111

20251202McKeownJPorph&Phalocyanins-AAMAccepted author manuscript, 2.75 MBLicence: Creative Commons: Attribution (CC-BY)

https://www.worldscientific.com/doi/10.1142/S1088424625501111Licence: Unspecified

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title = "The influence of metal cations on the formation of phthalocyanine/porphyrin heterodimers and nanoporous cocrystals",

abstract = "Porphyrin-containing Phthalocyanine Nanoporous Crystals (PNCs) have been prepared previously by the cocrystallisation of octa(2′,6′-di-iso-propyphenoxy)phthalocyanine [(dipPhO)8Pc] and its metalated derivatives with metal-free tetraphenylporphyrin (TPP). Here we report the effect of the central cations (M = H2, Co, Cu, Zn) on heterodimer formation, both in solution and in cocrystallisations, for all sixteen possible combinations of (dipPhO)8PcM with TPPM. UV/visible spectroscopy shows a clear trend of Cu2+ > 2H+ > Co2+ > Zn2+ for encouraging or discouraging heterodimer formation, which can be rationalised by the propensity of the metal cation to bind to axial ligands when incorporated into porphyrin or phthalocyanine macrocycles. Attempted cocrystallisations of all 16 (dipPhO)8PcM/TPPM combinations yielded 13 heterodimer-based PNCs, with only (dipPhO)8PcZn failing to provide a cocrystal with TPPM (Co, Cu, Zn). This study further demonstrates the remarkable efficiency of (dipPhO)8PcM in directing the structure of PNC cocrystallisations. It suggests a simple method for placing two metal cations of choice within van der Waals distance of one another within a well-defined, predictable crystal structure.",

keywords = "crystal, heterodimer, phthalocyanine, tetraphenylporphyrin",

author = "Shannah Kerrigan and Stamos, \{Nikolaos Angelos\} and Alexander Stiven and Emma Johnson and Benjamin Plevey and Catherine Newman and Nichol, \{Gary S.\} and Mckeown, \{Neil B.\}",

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T1 - The influence of metal cations on the formation of phthalocyanine/porphyrin heterodimers and nanoporous cocrystals

AU - Kerrigan, Shannah

AU - Stamos, Nikolaos Angelos

AU - Stiven, Alexander

AU - Johnson, Emma

AU - Plevey, Benjamin

AU - Newman, Catherine

AU - Nichol, Gary S.

AU - Mckeown, Neil B.

PY - 2025/12/2

Y1 - 2025/12/2

N2 - Porphyrin-containing Phthalocyanine Nanoporous Crystals (PNCs) have been prepared previously by the cocrystallisation of octa(2′,6′-di-iso-propyphenoxy)phthalocyanine [(dipPhO)8Pc] and its metalated derivatives with metal-free tetraphenylporphyrin (TPP). Here we report the effect of the central cations (M = H2, Co, Cu, Zn) on heterodimer formation, both in solution and in cocrystallisations, for all sixteen possible combinations of (dipPhO)8PcM with TPPM. UV/visible spectroscopy shows a clear trend of Cu2+ > 2H+ > Co2+ > Zn2+ for encouraging or discouraging heterodimer formation, which can be rationalised by the propensity of the metal cation to bind to axial ligands when incorporated into porphyrin or phthalocyanine macrocycles. Attempted cocrystallisations of all 16 (dipPhO)8PcM/TPPM combinations yielded 13 heterodimer-based PNCs, with only (dipPhO)8PcZn failing to provide a cocrystal with TPPM (Co, Cu, Zn). This study further demonstrates the remarkable efficiency of (dipPhO)8PcM in directing the structure of PNC cocrystallisations. It suggests a simple method for placing two metal cations of choice within van der Waals distance of one another within a well-defined, predictable crystal structure.

AB - Porphyrin-containing Phthalocyanine Nanoporous Crystals (PNCs) have been prepared previously by the cocrystallisation of octa(2′,6′-di-iso-propyphenoxy)phthalocyanine [(dipPhO)8Pc] and its metalated derivatives with metal-free tetraphenylporphyrin (TPP). Here we report the effect of the central cations (M = H2, Co, Cu, Zn) on heterodimer formation, both in solution and in cocrystallisations, for all sixteen possible combinations of (dipPhO)8PcM with TPPM. UV/visible spectroscopy shows a clear trend of Cu2+ > 2H+ > Co2+ > Zn2+ for encouraging or discouraging heterodimer formation, which can be rationalised by the propensity of the metal cation to bind to axial ligands when incorporated into porphyrin or phthalocyanine macrocycles. Attempted cocrystallisations of all 16 (dipPhO)8PcM/TPPM combinations yielded 13 heterodimer-based PNCs, with only (dipPhO)8PcZn failing to provide a cocrystal with TPPM (Co, Cu, Zn). This study further demonstrates the remarkable efficiency of (dipPhO)8PcM in directing the structure of PNC cocrystallisations. It suggests a simple method for placing two metal cations of choice within van der Waals distance of one another within a well-defined, predictable crystal structure.

KW - crystal

KW - heterodimer

KW - phthalocyanine

KW - tetraphenylporphyrin

U2 - 10.1142/S1088424625501111

DO - 10.1142/S1088424625501111

M3 - Article

AN - SCOPUS:105023645488

SN - 1088-4246

JO - Journal of porphyrins and phthalocyanines

JF - Journal of porphyrins and phthalocyanines

ER -

The influence of metal cations on the formation of phthalocyanine/porphyrin heterodimers and nanoporous cocrystals

Abstract

Keywords / Materials (for Non-textual outputs)

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