Recent advances in the supramolecular assembly of cyclophosphazene derivatives.

Cyclophosphazenes are a fascinating group of inorganic heterocyclic compounds whose rings are constituted by the repetition of phosphorus and nitrogen atoms. They have received particular attention due to their easy functionalization and thermal stability and as an excellent core for the preparation of advanced materials. Rigid trispirocyclic derivatives of cyclophosphazenes afford numerous supramolecular structures that are suitable for the formation of host-guest complexes with a variety of guest molecules such as gas molecules and molecular rotor compounds. Also, the donor nitrogen atoms of the cyclophosphazene ring can participate in non-covalent interactions such as hydrogen bonding and metal coordination. It can also be used in the construction of supramolecular dendrimeric or polymeric systems as either the starting compound or the carrier of supramolecular groups. Thus, cyclophosphazenes have been employed in the preparation of supramolecular systems for about past 30 years. This review focuses on the state of recent advances in the construction of cyclotriphosphazene-based supramolecular systems built by non-covalent interactions and their applications such as host-guest complexes, liquid crystals, coordination polymers and nanostructures. The future perspective of cyclophosphazene supramolecular assemblies is also discussed.

[1]  F. Yuksel,et al.  Synthesis, characterization, photophysical and intramolecular energy transfer properties of oxy-naphthylchalcone appended cyclotriphosphazene cores , 2020, Journal of Luminescence.

[2]  D. Atilla,et al.  New cyclotriphosphazene ligand containing imidazole rings and its one-dimensional copper(II) coordination polymer , 2020 .

[3]  M. Buzin,et al.  Investigation of hexakis[2-formylphenoxy]cyclotriphosphazene structure by single crystal X-ray diffraction and computer simulation , 2020 .

[4]  M. Dušek,et al.  Formation of a copper–copper bond in coordination of a cyclotriphosphazene ligand toward Cu(II): Structural, spectral and docking studies , 2020 .

[5]  C. Rogers,et al.  Regular 2-D Arrays of Surface-Mounted Molecular Switches: Switching Monitored by UV-vis and NMR Spectroscopy. , 2020, Journal of the American Chemical Society.

[6]  Xingping Zhou,et al.  Flexible, Self-Healing, and Fire-Resistant Polymer Electrolytes Fabricated via Photopolymerization for All-Solid-State Lithium Metal Batteries. , 2020, ACS macro letters.

[7]  D. Atilla,et al.  Synthesis, characterization and photophysical properties of cyclotriphosphazenes including heterocyclic rings , 2019 .

[8]  Bixin Jin,et al.  Supramolecular Hexagonal Platelet Assemblies with Uniform and Precisely-Controlled Dimensions. , 2019, Journal of the American Chemical Society.

[9]  H. Raissi,et al.  Microwave-assisted solvent-free synthesis and spectral and structural characterization of cyclotriphosphazene hexakis(o-tolylamide) , 2018, Zeitschrift für Naturforschung B.

[10]  Yao Wang,et al.  Structural diversities and gas adsorption properties of a family of rod-packing lanthanide–organic frameworks based on cyclotriphosphazene-functionalized hexacarboxylate derivatives , 2018 .

[11]  Süleyman Köytepe,et al.  Synthesis of Phenanthroline-Functionalized Phosphazene Based Metallosupramolecular Polymers and Their Stimuli-Responsive Properties , 2018, Journal of Inorganic and Organometallic Polymers and Materials.

[12]  Derya Davarcı Design and construction of one-dimensional coordination polymers based on the dispiro-dipyridyloxy-cyclotriphosphazene ligand , 2018 .

[13]  Y. Zorlu,et al.  Naphthalimide-cyclophosphazene combination: Synthesis, crystal structure, photophysics and solid-state fluorescence , 2017 .

[14]  Yabing He,et al.  A rare Pb9 cluster-organic framework constructed from a flexible cyclotriphosphazene-functionalized hexacarboxylate exhibiting selective gas separation , 2017 .

[15]  Aylin Uslu,et al.  Supramolecular structures of cis-tris-non-geminal glycol derivatives of cyclotriphosphazene and their thermosensitive behaviors , 2017 .

[16]  Elif Şenkuytu,et al.  New dispiro-dipyridyloxy-cyclotriphosphazene ligand and its Ag(I) coordination polymer: Structure and thermal stability , 2017 .

[17]  Serkan Yeşilot,et al.  Imidazole/benzimidazole-modified cyclotriphosphazenes as highly selective fluorescent probes for Cu2+: synthesis, configurational isomers, and crystal structures. , 2017, Dalton transactions.

[18]  J. Serrano,et al.  Mixed-Substituent Cyclophosphazenes with Calamitic and Polycatenar Mesogens. , 2017, Inorganic chemistry.

[19]  Pei‐Hua Zhao,et al.  Facile synthesis, spectroscopic characterization, and crystal structures of dioxybiphenyl bridged cyclotriphosphazenes , 2017 .

[20]  Y. Zorlu,et al.  Group 12 metal coordination polymers built on a flexible hexakis(3-pyridyloxy)cyclotriphosphazene ligand: Effect of the central metal ions on the construction of coordination polymers , 2017 .

[21]  Serkan Yeşilot,et al.  Stereochemical Aspects of Polyphosphazenes , 2017 .

[22]  S. Dogan,et al.  The reaction of N,N-spiro bridged octachlorobis(cyclotriphosphazene) with 1,3-propanediol: Comparison with 1,2-ethanediol , 2017 .

[23]  Yun-long Feng,et al.  Alkaline earth-based coordination polymers derived from a cyclotriphosphazene-functionalized hexacarboxylate , 2016 .

[24]  O. Dautel,et al.  Crystal structure of tris(binol)cyclotriphosphazene. A new clathration system , 2016 .

[25]  Yun-long Feng,et al.  A porous lanthanide metal–organic framework based on a flexible cyclotriphosphazene-functionalized hexacarboxylate exhibiting selective gas adsorption , 2016 .

[26]  C. Rogers,et al.  Bulk Inclusions of Pyridazine‐Based Molecular Rotors in Tris(o‐phenylenedioxy)cyclotriphosphazene (TPP) , 2016 .

[27]  V. Selvaraj,et al.  Cyclophosphazene based conductive polymer-carbon nanotube composite as novel supporting material for methanol fuel cell applications. , 2016, Journal of colloid and interface science.

[28]  Y. Zorlu,et al.  Silver(I) coordination polymers assembled from flexible cyclotriphosphazene ligand: structures, topologies and investigation of the counteranion effects. , 2016, Acta crystallographica Section B, Structural science, crystal engineering and materials.

[29]  V. Selvaraj,et al.  Development of ternary hexafluoroisopropylidenedianiline/cyclophosphazene/benzidine- disulfonic acid-carbon nanotubes (HFPA/CP/BZD-CNT) composite as a catalyst support for high performance alcohol fuel cell applications , 2016 .

[30]  V. Chandrasekhar,et al.  Molecular, 1D and 2D assemblies from hexakis(3-pyridyloxy)cyclophosphazene containing 20-membered metallamacrocyclic motifs. , 2016, Dalton transactions.

[31]  Kilian Muñiz,et al.  Titelbild: Strukturell definierte molekulare hypervalente Iod‐Katalysatoren für intermolekulare enantioselektive Reaktionen (Angew. Chem. 1/2016) , 2016 .

[32]  Yun-long Feng,et al.  A metal–organic framework based on cyclotriphosphazene-functionalized hexacarboxylate for selective adsorption of CO2 and C2H6 over CH4 at room temperature , 2015 .

[33]  C. Rogers,et al.  Arrays of Molecular Rotors with Triptycene Stoppers: Surface Inclusion in Hexagonal Tris(o-phenylenedioxy)cyclotriphosphazene. , 2015, The Journal of organic chemistry.

[34]  Serkan Yeşilot,et al.  Chiral configurations in cyclophosphazene chemistry , 2015 .

[35]  C. Rogers,et al.  Time-Resolved Fluorescence Anisotropy of Bicyclo[1.1.1]pentane/Tolane-Based Molecular Rods Included in Tris(o-phenylenedioxy)cyclotriphosphazene (TPP) , 2015, The journal of physical chemistry. C, Nanomaterials and interfaces.

[36]  Xi Chen,et al.  A three-dimensional complex with a one-dimensional cobalt-hydroxyl chain based on planar nonanuclear clusters showing spin-canted antiferromagnetism. , 2015, Inorganic chemistry.

[37]  H. Cui,et al.  Supramolecular nanostructures as drug carriers , 2015 .

[38]  A. Caminade,et al.  Supermolecular columnar liquid-crystalline phosphorus dendrimers decorated with sulfonamide derivatives. , 2014, Chemistry.

[39]  E. Doganci,et al.  Supramolecular inclusion complexes of a star polymer containing cholesterol end‐capped poly(ε‐caprolactone) arms with β‐cyclodextrin , 2014 .

[40]  P. Rinaldi,et al.  Structure and conformation of the medium-sized chlorophosphazene rings. , 2014, Inorganic chemistry.

[41]  C. Sánchez‐Somolinos,et al.  Photoresponsive Liquid-Crystalline Dendrimers Based on a Cyclotriphosphazene Core , 2014 .

[42]  F. Yuksel,et al.  Investigation of the structural properties of 2-naphthylamine substituted cyclotetraphosphazenes , 2014 .

[43]  A. Ajayaghosh,et al.  Cyclotriphosphazene appended porphyrins and fulleropyrrolidine complexes as supramolecular multiple photosynthetic reaction centers: steady and excited states photophysical investigation. , 2014, Physical chemistry chemical physics : PCCP.

[44]  Di Sun,et al.  Luminescent Response of One Anionic Metal–Organic Framework Based on Novel Octa-nuclear Zinc Cluster to Exchanged Cations , 2014 .

[45]  C. Rogers,et al.  Arrays of dipolar molecular rotors in Tris(o-phenylenedioxy) cyclotriphosphazene. , 2014, Topics in current chemistry.

[46]  Xiaohong Cheng,et al.  Synthesis and characterization of room temperature columnar mesogens of cyclotriphosphazene with Schiff base units , 2013 .

[47]  Xi Chen,et al.  Lanthanide coordination polymers with hexa-carboxylate ligands derived from cyclotriphosphazene as bridging linkers: synthesis, thermal and luminescent properties , 2013 .

[48]  F. Yuksel,et al.  The synthesis and characterization of 4-isopropylanilino derivatives of cyclotriphosphazene , 2013 .

[49]  Qun Xu,et al.  Silver nanoparticles-decorated polyphosphazene nanotubes: synthesis and applications. , 2013, Nanoscale.

[50]  G. Jameson,et al.  Flexible pyridyloxy-substituted cyclotetraphosphazene platforms linked by silver(I) , 2013 .

[51]  A. Zhang,et al.  Microbelts and flower-like particles of hexakis-(4-(5-styryl-1,3,4-oxazodiazol-2-yl)-phenoxy)-cyclotriphosphazene: self-assembly and photoreaction , 2013 .

[52]  V. Chandrasekhar,et al.  Metalation studies of 3- and 4-pyridyloxycyclophosphazenes: metallamacrocycles to coordination polymers. , 2013, Dalton transactions.

[53]  Bao Li,et al.  Temperature-controlled synthesis and luminescent properties of two novel coordination polymers modeled by hexa-carboxylate ligand derived from cyclotriphosphazene. , 2013, Dalton transactions.

[54]  J. Serrano,et al.  New liquid crystalline materials based on two generations of dendronised cyclophosphazenes. , 2012, Chemistry.

[55]  Jianping Ma,et al.  Coordination-driven synthesis of Ag(I) compounds based on a double emission ligand consisting of 1,3,4-oxadiazole and cyclotriphosphazene units , 2012 .

[56]  A. Zhang,et al.  1D nano- and microbelts self-assembled from the organic-inorganic hybrid molecules: oxadiazole-containing cyclotriphosphazene. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[57]  J. Serrano,et al.  Supermolecular liquid crystals with a six-armed cyclotriphosphazene core: from columnar to cubic phases. , 2011, Chemistry.

[58]  Anne-Martine S. Jackson,et al.  Synthesis and inclusion behavior of cyclotriphosphazene molecules with asymmetric spiro rings. , 2010, Dalton transactions.

[59]  K. Gordon,et al.  Excited states of Ru(II) and Re(I) bipyridyl complexes attached to cyclotriphosphazenes: a synthetic, spectroscopic, and computational study. , 2010, Inorganic chemistry.

[60]  R. Boomishankar,et al.  Aqueous chemistry of chlorocyclophosphazenes: phosphates {PO(2)}, phosphamides {P(O)NHR}, and the first phosphites {PHO} and pyrophosphates {(PO)(2)O} of these heterocycles. , 2010, Inorganic chemistry.

[61]  Peter G. Jones,et al.  Metallocyclo- and polyphosphazenes containing gold or silver: thermolytic transformation into nanostructured materials. , 2009, Chemistry.

[62]  Jingping Zhang,et al.  Design of an organic zeolite toward the selective adsorption of small molecules at the dispersion corrected density functional theory level. , 2009, The journal of physical chemistry. B.

[63]  I. Vorontsov,et al.  X-ray crystal structures and DFT calculations of differently charged aminocyclophosphazenes , 2009 .

[64]  D. Reinhoudt,et al.  From supramolecular chemistry to nanotechnology: Assembly of 3D nanostructures , 2009 .

[65]  M. Waterland,et al.  Metal-metal communication in copper(II) complexes of cyclotetraphosphazene ligands. , 2008, Inorganic chemistry.

[66]  V. G. Tsirel’son,et al.  Mono-and diphenoxy-substituted cyclotriphosphazenes: The molecular structure and interatomic interactions , 2008 .

[67]  Jianwei Xu,et al.  Hydrogen bond‐directed self‐assembly of peripherally modified cyclotriphosphazenes with a homeotropic liquid crystalline phase , 2008 .

[68]  R. Davidson,et al.  The first coordination polymer containing a chiral cyclotriphosphazene ligand , 2008 .

[69]  V. Chandrasekhar,et al.  Synthesis, structure and metallation of spiro-N3P3(O2C12H8)(OC5H4N-2)4: A heptacoordinate Co(II) in the molecular structure of N3P3(O2C12H8)(OC5H4N-2)4 · Co(NO3)2 , 2008 .

[70]  J. Serrano,et al.  Cyclotriphosphazene as a dendritic core for the preparation of columnar supermolecular liquid crystals , 2006 .

[71]  Bernd Jaeckel,et al.  Open‐Pore Organic Material for Retaining Radioactive I2 and CH3I , 2006 .

[72]  J. Serrano,et al.  Columnar mesomorphic organizations in cyclotriphosphazenes. , 2005, Journal of the American Chemical Society.

[73]  S Bracco,et al.  Methane and carbon dioxide storage in a porous van der Waals crystal. , 2005, Angewandte Chemie.

[74]  Kenzo Inoue,et al.  Self-Assembly of Hexakis(4-pyridylmethoxy)cyclotriphosphazene and 1,4-Anthracenedicarboxylic Acid : Structure and Inclusion Behavior , 2002 .

[75]  K. Moriya,et al.  31P and 13C NMR Studies of a Liquid-Crystalline Cyclotriphosphazene Derivative: Orientational Characteristics and Contrasting Shielding Anisotropies for Inorganic and Organic Moieties , 2001 .

[76]  H. Allcock,et al.  Inclusion adduct formation between tris(o-phenylenedioxy)cyclotriphosphazene and poly(ethylene oxide) or polyethylene , 1997 .

[77]  Masahiro Kato,et al.  Thermal and Structural Study on Liquid-Crystalline Phase Transition in Hexakis(4-(4‘-alkyloxy)biphenoxy)cyclotriphosphazene , 1997 .

[78]  Harry R. Allcock,et al.  Tris(o-phenylenedioxy)cyclotriphosphazene: the clathration-induced monoclinic to hexagonal solid-state transition , 1986 .

[79]  H. Allcock Recent advances in phosphazene (phosphonitrilic) chemistry , 1972 .