Fluorescent organic cages and their applications

Abstract

Organic cages are an emerging subclass of crystalline porous materials with structural tunability, modularity, and processibility, having exhibited potential in applications such as molecular recognition, gas adsorption, catalysis, and other fields. Fluorescence can be easily introduced into organic cages by incorporating fluorescent building blocks. The diversity of fluorescent building blocks and well-developed cage construction methods allowed the booming of fluorescent organic cages. More importantly, incorporating fluorescent properties into organic cages can further expand their application areas, especially in fields such as biological imaging and luminescent devices. The cavity of organic cages endows them with extra confined space to accommodate bioactive species or drugs compared to fluorescent small molecules. Compared to their framework counterparties, organic cages with well-characterized structures exhibit better processability, allowing their use in applications beyond solutions. In this review, we summarize the latest progress on fluorescent organic cages, focusing on their construction methods and the recent advances in their applications.

Keywords

Organic cages / fluorescent / synthesis strategies / applications

References

[1] Duan YC,Gao Y.Fluorescence, phosphorescence, or delayed fluorescence? - A theoretical exploration on the reason why a series of similar organic molecules exhibit different luminescence types.J Phys Chem C2018;122:23091-101

[2] Fang M,Li Z.Light emission of organic luminogens: generation, mechanism and application.Prog Mater Sci2022;125:100914

[3] Ockwig NW,O’Keeffe M.Reticular chemistry: occurrence and taxonomy of nets and grammar for the design of frameworks.Acc Chem Res2005;38:176-82

[4] Férey G.Hybrid porous solids: past, present, future.Chem Soc Rev2008;37:191-214

[5] Xue R,Wang T.Fluorescence properties and analytical applications of covalent organic frameworks.Anal Methods2017;9:3737-50

[6] Sun YL,Ren C.Highly emissive organic cage in single-molecule and aggregate states by anchoring multiple aggregation-caused quenching dyes.ACS Appl Mater Interfaces2022;14:53567-74

[7] Yang X,Stoddart JF.Porous organic cages.Chem Rev2023;123:4602-34 PMCID:PMC10141292

[8] Wang H,Sun N,Jiang J.Post-synthetic modification of porous organic cages.Chem Soc Rev2021;50:8874-86

[9] Hu D,Liu M.Recent advances in the applications of porous organic cages.Chem Commun2022;58:11333-46

[10] Tozawa T,Swamy SI.Porous organic cages.Nat Mater2009;8:973-8

[11] Wang Z,Yong T,Zhang C.Multicolor tunable polymeric nanoparticle from the tetraphenylethylene cage for temperature sensing in living cells.J Am Chem Soc2020;142:512-9

[12] Chen L,Fu E.A donor–acceptor cage for thermally activated delayed fluorescence: toward a new kind of TADF exciplex emitters.ACS Mater Lett2023;5:1450-5

[13] Acharyya K.A fluorescent organic cage for picric acid detection.Chem Commun2014;50:15788-91

[14] Dong J,Yang K.Enhanced biological imaging via aggregation-induced emission active porous organic cages.ACS Nano2022;16:2355-68

[15] Liyana Gunawardana VW,Wang H.Crystalline nanoparticles of water-soluble covalent basket cages (CBCs) for encapsulation of anticancer drugs.Angew Chem Int Ed Engl2023;62:e202306722 PMCID:PMC10528532

[16] Pérez-Márquez LA,García-Rodríguez R,Carrillo R.A fluorescent cage for supramolecular sensing of 3-nitrotyrosine in human blood serum.Angew Chem Int Ed Engl2022;61:e202205403 PMCID:PMC9401051

[17] Lin CY,Hung CM.Entropy-driven charge-transfer complexation yields thermally activated delayed fluorescence and highly efficient OLEDs.Nat Chem2024;16:98-106

[18] Zahra T,Jamal H,Akhtar F.A review of biocompatible polymer-functionalized two-dimensional materials: emerging contenders for biosensors and bioelectronics applications.Anal Chim Acta2024;1316:342880

[19] Lustig WP,Rudd ND,Li J.Metal-organic frameworks: functional luminescent and photonic materials for sensing applications.Chem Soc Rev2017;46:3242-85

[20] Wang S,Huang H,Chen X.Porous organic polymers as a platform for sensing applications.Chem Soc Rev2022;51:2031-80

[21] Raja Lakshmi, P.; Nanjan, P.; Kannan, S.; Shanmugaraju, S. Recent advances in luminescent metal–organic frameworks (LMOFs) based fluorescent sensors for antibiotics.Coord Chem Rev2021;435:213793

[22] Dey S,Shukla A.Thermally activated delayed fluorescence and room-temperature phosphorescence in asymmetric phenoxazine-quinoline (D2–A) conjugates and dual electroluminescence.J Phys Chem C2022;126:5649-57

[23] Tao Y,Chen T.Thermally activated delayed fluorescence materials towards the breakthrough of organoelectronics.Adv Mater2014;26:7931-58

[24] Zhang H,Turley AT.Aggregate science: from structures to properties.Adv Mater2020;32:e2001457

[25] Maji S,Samanta K.Emissive click cages.Chemistry2023;29:e202301985

[26] Qiu F,Wang W,Yuan D.Highly stable sp² carbon-conjugated porous organic cages.CCS Chem2024;6:149-56

[27] Montà-González G,Martínez-Máñez R.Purely covalent molecular cages and containers for guest encapsulation.Chem Rev2022;122:13636-708 PMCID:PMC9413269

[28] Borse RA,Yuan D.Progress of porous organic cages in photo/electrocatalytic energy conversion and storage applications.Energy Environ Sci2024;17:1307-29

[29] Guo Z,Wang H.Drum-like metallacages with size-dependent fluorescence: exploring the photophysics of tetraphenylethylene under locked conformations.J Am Chem Soc2021;143:9215-21

[30] Liu Y,Guo Y.Topological effect on fluorescence emission of tetraphenylethylene-based metallacages.Chinese Chemical Letters2023;34:108531

[31] Feng HT,Xiong JB,Tang BZ.Macrocycles and cages based on tetraphenylethylene with aggregation-induced emission effect.Chem Soc Rev2018;47:7452-76

[32] Wang H,Lam JW.AIE luminogens: emission brightened by aggregation.Mater Today2015;18:365-77

[33] Zou D,Long D.Molecular cage with dual outputs of photochromism and luminescence both in solution and the solid state.ACS Appl Mater Interfaces2023;15:13545-53

[34] Zheng X,Zhang C.Self-assembly of a highly emissive pure organic imine-based stack for electroluminescence and cell imaging.J Am Chem Soc2019;141:4704-10

[35] Li Y,Feng R.Reticular modulation of piezofluorochromic behaviors in organic molecular cages by replacing non-luminous components.Angew Chem Int Ed Engl2024;63:e202403646

[36] Zhang C,Tan L.A porous tricyclooxacalixarene cage based on tetraphenylethylene.Angew Chem Int Ed Engl2015;54:9244-8

[37] Duan H,Li Q.Host-guest recognition and fluorescence of a tetraphenylethene-based octacationic cage.Angew Chem Int Ed Engl2020;59:10101-10

[38] Duan H,Hao H,Cao L.Efficient photoinduced energy and electron transfers in a tetraphenylethene-based octacationic cage through host-guest complexation.ACS Appl Mater Interfaces2021;13:16837-45

[39] Feng X,Jiang J,Ke Z.Perylene diimide based imine cages for inclusion of aromatic guest molecules and visible-light photocatalysis.ChemPhotoChem2019;3:1014-9

[40] Konopka M,Ulrich S.Tuning the solubility of self-assembled fluorescent aromatic cages using functionalized amino acid building blocks.Front Chem2019;7:503 PMCID:PMC6647868

[41] Bhandari P,Saha R.Enhancing fluorescence in both solution and solid states induced by imine cage formation.Chemistry2024;30:e202303101

[42] Drożdż W,Kotras C.Generation of multicomponent molecular cages using simultaneous dynamic covalent reactions.Chemistry2017;23:18010-8

[43] Wang Z,Zhai TL.Networked cages for enhanced CO₂ capture and sensing.Adv Sci2018;5:1800141 PMCID:PMC6051374

[44] Cheng L,Duan Y.Adaptive chirality of an achiral cage: chirality transfer, induction, and circularly polarized luminescence through aqueous host–guest complexation.CCS Chem2021;3:2749-63

[45] Xu W,Chang X.Polyanion and anionic surface monitoring in aqueous medium enabled by an ionic host-guest complex.Sens Actuators B Chem2021;340:129916

[46] Duan H,Zhang M,Cao L.On-off-on fluorescence detection for biomolecules by a fluorescent cage through host-guest complexation in water.Chin Chem Lett2022;33:2459-63

[47] Duan Y,Cheng L.A fluorescent, chirality-responsive, and water-soluble cage as a multifunctional molecular container for drug delivery.Org Biomol Chem2022;20:3998-4005

[48] Cao F,Li Q.A tetraphenylethene-based hexacationic molecular cage with an open cavity.Chem Commun2022;58:13389-92

[49] Duan H,Li Q,Wang P.Recognition and chirality sensing of guanosine-containing nucleotides by an achiral tetraphenylethene-based octacationic cage in water.Chin Chem Lett2024;35:108878

[50] Zhao Y,Guo F.White light emissive tetraphenylethene molecular cage-based hybrid nanoparticles for intracellular long-term imaging.ACS Appl Nano Mater2024;7:14549-56

[51] Zhu ZH,Chen J.A biocompatible pure organic porous nanocage for enhanced photodynamic therapy.Mater Horiz2023;10:4868-81

[52] An L,Smith PT,Chang CJ.Synergistic porosity and charge effects in a supramolecular porphyrin cage promote efficient photocatalytic CO₂ reduction.Angew Chem Int Ed Engl2023;62:e202209396 PMCID:PMC9868116

[53] Kagan NE,Marrifield RB.strati-Bisporphyrins. A novel cyclophane system.J Am Chem Soc1977;99:5484-6

[54] Cen T,Zhang Z,Li S.Flexible porphyrin cages and nanorings.J Porphyrins Phthalocyanines2018;22:726-38

[55] Liu C,Wang C.Elucidating heterogeneous photocatalytic superiority of microporous porphyrin organic cage.Nat Commun2020;11:1047 PMCID:PMC7044162

[56] Hong S,Jia J.Porphyrin boxes: rationally designed porous organic cages.Angew Chem Int Ed Engl2015;54:13241-4

[57] Chen H,Myong MS.Triplet-triplet annihilation upconversion in a porphyrinic molecular container.J Am Chem Soc2023;145:10061-70

[58] Shi Y,Xiao H.Selective extraction of C₇₀ by a tetragonal prismatic porphyrin cage.J Am Chem Soc2018;140:13835-42

[59] An JM,Kim D.Recent advances in two-photon absorbing probes based on a functionalized dipolar naphthalene platform.Org Biomol Chem2020:4288-97

[60] Liu C,Qi D.Enantioselective assembly and recognition of heterochiral porous organic cages deduced from binary chiral components.Chem Sci2022;13:7014-20 PMCID:PMC9200113

[61] Huang HH,Prescimone A.Porous shape-persistent rylene imine cages with tunable optoelectronic properties and delayed fluorescence.Chem Sci2021;12:5275-85 PMCID:PMC8179562

[62] Jia F,Yang LP.Naphthocage: a flexible yet extremely strong binder for singly charged organic cations.J Am Chem Soc2019;141:4468-73

[63] Jia F,Yang LP.Redox-responsive host-guest chemistry of a flexible cage with naphthalene walls.J Am Chem Soc2020;142:3306-10

[64] Xu Z,Kim SK,Kim KS.Induction-driven stabilization of the anion-π interaction in electron-rich aromatics as the key to fluoride inclusion in imidazolium-cage receptors.Chemistry2011;17:1163-70

[65] Wang F,Kong Q.Recent studies focusing on the development of fluorescence probes for zinc ion.Coord Chem Rev2021;429:213636

[66] Sun N,Jin Y.Porous pyrene organic cage with unusual absorption bathochromic-shift enables visible light photocatalysis.CCS Chem2022;4:2588-96

[67] Ge C,Chen Z.Self-assembled pure covalent tubes exhibiting circularly polarized luminescence.Angew Chem Int Ed Engl2024;63:e202408056

[68] Li Y,Wang M.Two pyrene-based cagearene constitutional isomers: synthesis, separation, and host–guest chemistry.Org Chem Front2024;11:4992-6

[69] Al Kelabi, D.; Dey, A.; Alimi, L. O.; Piwoński, H.; Habuchi, S.; Khashab, N. M. Photostable polymorphic organic cages for targeted live cell imaging.Chem Sci2022;13:7341-6 PMCID:PMC9214840

[70] Dai C,Liu B.Organic cages with dual emission promoted by cage-like structure for ratiometric sensing of hypochlorous acid.Microchem J2024;204:110967

[71] Dai C,Yan XP.Facile room temperature synthesis of ultra-small sized porous organic cages for fluorescent sensing of copper ion in aqueous solution.J Hazard Mater2021;416:125860

[72] Dai C,Tang SP,Liu B.Fluorescent porous organic cage with good water solubility for ratiometric sensing of gold(III) ion in aqueous solution.Anal Chim Acta2022;1192:339376

[73] Mastalerz M,Oppel IM.A salicylbisimine cage compound with high surface area and selective CO₂/CH₄ adsorption.Angew Chem Int Ed Engl2011;50:1046-51

[74] Schneider MW,Ott H.Periphery-substituted [4+6] salicylbisimine cage compounds with exceptionally high surface areas: influence of the molecular structure on nitrogen sorption properties.Chemistry2012;18:836-47

[75] Alexandre PE,Rominger F,Schröder RR.A robust porous quinoline cage: transformation of a [4+6] salicylimine cage by povarov cyclization.Angew Chem Int Ed Engl2020;59:19675-9 PMCID:PMC7689861

[76] Bureš F.Fundamental aspects of property tuning in push–pull molecules.RSC Adv2014;4:58826-51

[77] Šimon P,Burešová Z.Centripetal triazine chromophores: towards efficient two-photon absorbers and highly emissive polyimide films.J Mater Chem C2023;11:7252-61

[78] Hu J,Zhu H.Photophysical properties of intramolecular charge transfer in a tribranched donor-π-acceptor chromophore.Chemphyschem2015;16:2357-65

[79] Padalkar VS,Sekar N.Synthesis and photo-physical properties of fluorescent 1,3,5-triazine styryl derivatives.Chem Cent J2011;5:77 PMCID:PMC3277491

[80] Zhang H,Wang DX.Triazine- and binaphthol-based chiral macrocycles and cages: synthesis, structure, and solid-state assembly.J Org Chem2022;87:3491-7

[81] Ding H,Li B.Targeted synthesis of a large triazine-based [4+6] organic molecular cage: structure, porosity and gas separation.Chem Commun2015;51:1976-9

[82] Liu Z,Su L.Efficient intramolecular charge-transfer fluorophores based on substituted triphenylphosphine donors.Angew Chem Int Ed Engl2021;60:15049-53

[83] Yu Q.Design and synthesis of triphenylphosphine-based donor-π-acceptor fluorophores with strong aggregation-induced emission and enantiomer-paired flower-like stacking.Dyes Pigm2024;223:111903

[84] Gajula RK,Chakraborty M,Prakash MJ.An imine linked fluorescent covalent organic cage: the sensing of chloroform vapour and metal ions, and the detection of nitroaromatics.New J Chem2021;45:4810-22

[85] Ren H,Ding X,Wang H.High fluorescence porous organic cage for sensing divalent palladium ion and encapsulating fine palladium nanoparticles.Chin J Chem2022;40:385-91

[86] Hu Y,Xu Z.Three-dimensional organic cage with narrowband delayed fluorescence.Sci China Chem2020;63:897-903

[87] Wang ZC,Yu H,Tang LL.A benzothiadiazole-based self-assembled cage for cadmium detection.Molecules2023;28:1841 PMCID:PMC9967857

[88] Zhang RF,Liu YA.A shape-persistent cryptand for capturing polycyclic aromatic hydrocarbons.J Org Chem2016;81:5649-54

[89] Wang Z,Guo F.Self-similar chiral organic molecular cages.Nat Commun2024;15:670 PMCID:PMC10803742

[90] Zhao X,Guo L.General and modular synthesis of covalent organic cages for efficient molecular recognition.Angew Chem Int Ed Engl2024;63:e202411613

[91] Xu Z,Liu Y,Jiang S.Design and assembly of porous organic cages.Chem Commun2024;60:2261-82

[92] Brand MC,Pegg JT.Photoresponsive organic cages-computationally inspired discovery of azobenzene-derived organic cages.J Am Chem Soc2024;146:30332-9 PMCID:PMC11544616

[93] Berardo E,Miklitz M,Jelfs KE.Computational screening for nested organic cage complexes.Mol Syst Des Eng2020;5:186-96

[94] Trzaskowski, B.; Martínez, J. P.; Sarwa, A.; Szyszko, B.; Goddard, W. A. 3rd. Argentophilic interactions, flexibility, and dynamics of pyrrole cages encapsulating silver(I) clusters.J Phys Chem A2024;128:3339-50 PMCID:PMC11077489

[95] Tarzia A,Jelfs KE.Systematic exploration of accessible topologies of cage molecules via minimalistic models.Chem Sci2023;14:12506-17 PMCID:PMC10646940

[96] Santolini V,Berardo E.Topological landscapes of porous organic cages.Nanoscale2017;9:5280-98

[97] Berardo E,Miklitz M.An evolutionary algorithm for the discovery of porous organic cages.Chem Sci2018;9:8513-27 PMCID:PMC6251339

[98] Turcani L,Szczypiński FT.stk: An extendable Python framework for automated molecular and supramolecular structure assembly and discovery.J Chem Phys2021;154:214102

[99] Turcani L,Jelfs KE.stk: A python toolkit for supramolecular assembly.J Comput Chem2018;39:1931-42 PMCID:PMC6585955

[100] Berardo E,Turcani L.Computationally-inspired discovery of an unsymmetrical porous organic cage.Nanoscale2018;10:22381-8

[101] Jones JT,Wu X.Modular and predictable assembly of porous organic molecular crystals.Nature2011;474:367-71

[102] Slater AG,Pulido A.Computationally-guided synthetic control over pore size in isostructural porous organic cages.ACS Cent Sci2017;3:734-42 PMCID:PMC5532722

[103] Del Regno, A.; Siperstein, F. R. Organic molecules of intrinsic microporosity: characterization of novel microporous materials.Micropor Mesopor Mat2013;176:55-63

[104] Evans JD,Hill MR.Molecular design of amorphous porous organic cages for enhanced gas storage.J Phys Chem C2015;119:7746-54

[105] Abbott LJ,Del Regno A.Characterizing the structure of organic molecules of intrinsic microporosity by molecular simulations and X-ray scattering.J Phys Chem B2013;117:355-64

[106] Jiang S,Holden D.Molecular dynamics simulations of gas selectivity in amorphous porous molecular solids.J Am Chem Soc2013;135:17818-30

[107] Miklitz M.pywindow: automated structural analysis of molecular pores.J Chem Inf Model2018;58:2387-91 PMCID:PMC6307083

[108] Miklitz M,Clowes R,Cooper AI.Computational screening of porous organic molecules for xenon/krypton separation.J Phys Chem C2017;121:15211-22

[109] Chen L,Chong SY.Separation of rare gases and chiral molecules by selective binding in porous organic cages.Nat Mater2014;13:954-60

[110] Zhao D,Su Q,Zhou J.Lysozyme adsorption on porous organic cages: a molecular simulation study.Langmuir2020;36:12299-308

[111] Day GM.Energy-structure-function maps: cartography for materials discovery.Adv Mater2018;30:e1704944

[112] Gayathri P,Al-Sehemi AG.Triphenylamine-based stimuli-responsive solid state fluorescent materials.New J Chem2020;44:8680-96

[113] Luo W.Photo-responsive fluorescent materials with aggregation-induced emission characteristics.Adv Opt Mater2020;8:2001362

[114] Hu Y,Wang X,Huang F.Three-dimensional organic cage with aggregation-induced delayed fluorescence.Chin Chem Lett2021;32:1017-9

[115] Yu H,Luo S.A reusable fluorescent molecular self-assembly cage for simultaneous detection and recycling of silver(I) ion.Chem Asian J2024;19:e202300872

[116] Ren H,Yang W.Sensitive and selective sensor based on porphyrin porous organic cage fluorescence towards copper ion.Dyes Pigm2022;200:110117

[117] Zhao X,Zhang J.A hexapyrrolic molecular cage and the anion-binding studies in chloroform.J Mol Struct2023;1293:136232

[118] Bian L,Liu J,Wu L.Luminescent chiral triangular prisms capable of forming double helices for detecting traces of acids and anion recognition.J Mater Chem C2022;10:15394-9

[119] Pan J,Bao F.Multiple fluorescence color transitions mediated by anion-π interactions and C-F covalent bond formation.Chin Chem Lett2023;34:107519

[120] Della-Negra O,Dutasta JP,Martinez A.Fluorescence detection of the persistent organic pollutant chlordecone in water at environmental concentrations.Chemistry2023;29:e202203887

[121] Acharyya K,Mondal B,Mukherjee PS.Building block dependent morphology modulation of cage nanoparticles and recognition of nitroaromatics.Chemistry2017;23:8482-90

[122] Sharma V,Srivastava P,Bharadwaj PK.Peripheral fluorophore functionalized shape-persistent [2+3] organic cage for highly selective detection of picric acid.ChemistrySelect2019;4:7991-5

[123] Tao R,Zhao T.Cage-confinement induced emission enhancement.J Phys Chem Lett2022;13:6604-11

[124] Fantozzi N,Insuasty A.Selective detection of choline in pseudophysiological medium with a fluorescent cage receptor.Org Lett2023;25:2444-9

[125] Song H,Pan Y.Covalent organic nanocage with aggregation induced emission property and detection for Hg²⁺ as fluorescence sensors.Dyes Pigm2023;219:111584

[126] Feng H,Gu X.White-light emission of a binary light-harvesting platform based on an amphiphilic organic cage.Chem Mater2018;30:1285-90

[127] Mahto AK,Mandal A,Sarkar M.Breaking of J-aggregates in fluorescent covalent organic cage molecular materials through solid state grinding with metal salts: chemo-sensing and light-emitting diode applications.ACS Appl Opt Mater2024;2:394-404

[128] Sarkar K,Dastidar P.Self-assembly of spherical organic molecules to form hollow vesicular structures in water for encapsulation of an anticancer drug and its release.Chem Asian J2019;14:1992-9

[129] Dong Y,Duan Y.Dual responses of fluorescence and circular dichroism for antibiotics by a cationic cage in water.Synlett2024;35:109-12

[130] Zhang Y,Shi X.Pyrgos[n]cages: Redefining antibacterial strategy against drug resistance.Sci Adv2024;10:eadp4872 PMCID:PMC11277403

[131] Benke BP,Kim Y.Iodide-selective synthetic ion channels based on shape-persistent organic cages.J Am Chem Soc2017;139:7432-5