Preparation of 1，3-Alternate Calix［4］arene Derivatives and Their Hydrogen-Bonding Polymerization

doi:10.19894/j.issn.1000-0518.250029

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (3): 396-405.DOI: 10.19894/j.issn.1000-0518.250029

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Preparation of 1，3-Alternate Calix［4］arene Derivatives and Their Hydrogen-Bonding Polymerization

Xu WANG¹, Jin-Yu LI², Cai-Hong ZHANG²()

^1.Sci-Tech Information and Strategic Research Center of Shanxi Province，Taiyuan 030024，China
^2.College of Chemistry and Chemical Engineering，Shanxi University，Taiyuan 030006，China

Received:2015-01-15 Accepted:2025-02-25 Published:2025-03-01 Online:2025-04-11
Contact: Cai-Hong ZHANG
About author:chzhang@sxu.edu.cn
Supported by:
Shanxi Scholarship Council of China(2023-026)

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Abstract

Abstract:

Hydrogen bonds have directionality and are a common form of supramolecular assembly in tubular， linear， and network-like three-dimensional structures. In the study， 1，3-alternating-25，26，27，28-tetrapropyl cup［4］arene was used as the starting material， with aromatic thiophene rings incorporated to deepen its cavity and enhance its rigid structure. The two alternating arms were modified with different functional groups （including —COOH， —CONH?， and —COOCH?）， forming typical 1，3-alternate calix［4］arene supramolecular structural units. The carboxylic acid and amide derivatives of 1，3-alternate ［4］arene underwent hydrogen bonding polymerization， which， as observed by scanning electron microscopy （SEM）， led to the formation of one-dimensional tubular polymers. The effects of steric hindrance， solvent environment， and concentration on hydrogen bond polymerization were investigated. Once the polymers were formed， they affected their luminescent properties and thermal stability： Infrared spectra of them in solutions showed significant hydrogen bonding polymerization； Their solid-state fluorescence exhibited a marked red shift （＞25 nm） compared to ester derivatives， with a high quantum yield （＞20%）； And they demonstrated good thermal stability， over 370 ℃， about 35 ℃ higher than that of ester derivatives. This study laid the foundation for the application of 1，3-alternate ［4］arene polymers in photothermal materials.

Key words: 1, 3-Alternating calix［4］arene, Hydrogen bond polymerization, One-dimensional tubular supramolecular polymer, Solid-state fluorescence, Thermal stability

CLC Number:

O625

Xu WANG, Jin-Yu LI, Cai-Hong ZHANG. Preparation of 1，3-Alternate Calix［4］arene Derivatives and Their Hydrogen-Bonding Polymerization[J]. Chinese Journal of Applied Chemistry, 2025, 42(3): 396-405.

Figures/Tables 9

Fig.1 Synthesis route for carboxylic acid（1-1）， amide（1-2）， and ester （1-3） derivatives of 1，3-alternating calix［4］arene

Fig.2 Structures and self-assembly of 1，3-alternating calix［4］arene carboxylic acid， amide， and ester derivatives

Fig.3 Self-assembly of carboxylic acid （A， D）， amide （B， E） and ester （C， F） derivatives of 1，3-alternate calix［4］arene in V（THF）∶V（n-hexane）=1∶1 solution

Fig.4 The structure of 1，3-alternate calix［4］arene carboxylic acid derivatives with different length of alkoxy

Fig.5 SEM images of 1，3-alternate calix［4］arene carboxylic acid derivatives

Fig.6 FT-IR spectra of 1，3-alternate calix［4］arene carboxylic acid （A）， amide （B） and ester （C） derivatives in V（THF）∶V（n-hexane）=1∶1 solution （6×10?? mol/L）

Table 1 UV absorption and fluorescence spectroscopic data of 1，3-alternate calix［4］arene carboxylic acid， amide and ester derivatives

Compound	Solvent	Absorption wavelength/nm	ε/（L·mol?¹·cm?¹）	Emission wavelength/nm	?
1-1	THF	325	8.98×10⁴	395	0.28
	DMF	323	6.89×10⁴	411	0.31
	DMSO	324	6.16×10⁴	418	0.37
	Solid			443	0.28
1-2	THF	321	5.55×10⁴	390	0.23
	DMF	326	5.97×10⁴	402	0.24
	DMSO	328	9.05×10⁴	407	0.27
	Solid			446	0.20
1-3	THF	325	8.56×10⁴	396	0.26
	DMF	329	8.33×10⁴	418	0.34
	DMSO	331	8.30×10⁴	425	0.31
	Solid			438	0.14

Fig.7 UV absorption and normalized fluorescence spectra for carboxylic acid （A）， amide （B） and ester （C） derivatives of 1，3-alternate calix［4］arene

Fig.8 Thermogravimetric analysis （TGA） for carboxylic acid （A）， amide （B） and ester （C） derivatives of 1，3-alternate calix［4］arene

References 38

1	KANG S， KIM G H， PARK S J. Conjugated block copolymers for functional nanostructures［J］. Acc Chem Res， 2022， 55（16）： 2224-2234.
2	BUJOSA S， RUBERT L， ROTGER C， et al. Modulating self-assembly and polymorph transitions in bisdendronized squaramides［J］. Commun Chem， 2024， 7（1）： 296.
3	裴强，丁爱祥，吴晋晋. 基于分子内三中心氢键的超分子组装体系及其应用［J］. 有机化学， 2021， 41（1）： 105.
	PEI Q， DING A X， WU J J. Supramolecular assembly system based on intramolecular hydrogen bonds and its application［J］. Chin J Org Chem， 2021， 41（1）： 105.
4	DATTA S， TAKAHASHI S， YAGAI S. Nanoengineering of curved supramolecular polymers： toward single-chain mesoscale materials［J］. Acc Mater Res， 2022， 3（2）： 259-271.
5	王秀凤，张莉，刘鸣华. 超分子凝胶：结构多样性与超分子手性［J］. 物理化学学报， 2016， 32（1）： 227-238.
	WANG X F， ZHANG L， LIU M H. Supramolecular gels： structural diversity and supramolecular chirality［J］. Acta Phys Chim Sin， 2016， 32（1）： 227-238.
6	ZHANG N， WANG L， WANG H， et al. Self-assembled one-dimensional porphyrin nanostructures with enhanced photocatalytic hydrogen generation［J］. Nano Lett， 2018， 18（1）： 560-566.
7	DAI X J， LI C C， LI C J. Carbonyl umpolung as an organometallic reagent surrogate［J］. Chem Soc Rev， 2021， 50： 10733-10742.
8	CHO H H， KIM S H. A versatile protocol for the preparation of highly hindered aryl ketones using organozinc reagents［J］. Bull Korean Chem Soc， 2012， 33（9）： 3083-3086.
9	PARK K M， LEE E， PARK C S， et al. Tube-type coordination polymers： two-and four-silver （Ⅰ）-mediated linear networking of calix ［4］ arene tetracarboxylates［J］. Inorg Chem， 2011， 50（23）： 12085-12090.
10	KRAJANGSRI S， MUANGSIN N， PULPOKA B. Impact of binding positions of 1，3-alternate calix ［4］ arene tetrabenzoic acids on geometry of coordination polymers［J］. J Inclusion Phenom Macrocyclic Chem， 2021， 101（3）： 195-204.
11	LEE E， JU H， LEE S S， et al. Tubular arrangement of 1， 3-alternate calix［4］ arene with bipyridines： a platform for ［2+2］ photocyclization［J］. Cryst Growth Des， 2013， 13（3）： 992-995.
12	WANG W， GONG S， CHEN Y， et al. Fibriform one-dimensional hydrogen-bonded network composed of 1，2-alt calix ［4］ arene tetra acetic acid［J］. New J Chem， 2005， 29（11）： 1390-1392.
13	LAZAR A， DANYLYUK O， SUWINSKA K， et al. Assembly of a novel supramolecular synthon of calix ［4］ arene presenting four carboxylic acids［J］. Chem Commun， 2006 （8）： 903-905.
14	贾彦荣，付宏宇，夏敏. 具有力致变色性能的有机固体荧光分子的研究进展［J］. 浙江理工大学学报（自然科学版）， 2020， 43（3）： 401-412.
	JIA Y R， FU H Y， XIA M. Progress on organic solid fluorescent molecules with force chromochromic properties［J］. J Zhejiang Sci-Technol Univ （Nat Sci Ed）， 2020， 43（3）： 401-412.
15	COMERON J F， FRECHET J. Photogeneration of organic-bases from ortho-nitrobenzyl-derived carbamates［J］. J Am Chem Soc， 1991， 113（11）： 4303-4313.
16	ELEWA A M. Hydrogen-bonded organic frameworks （HOFs） from design to environmental application［J］. J Ind Eng Chem， 2025， 145： 169-190.
17	LEE J H， KIM Y， KIM G， et al. Synthesis of porphyrin derivatives bearing six carboxylic acids for the formation of three-dimensional hydrogen-bonded network structures［J］. Chem-Eur J， 2025： e202404280.
18	HAKOBYAN R M， SHAHKHATUNI A G， POLYNSKI M V， et al. The role of the nitro group on the formation of intramolecular hydrogen bond in the methyl esters of 1-vinyl-nitro-pyrazolecarboxylic acids［J］. J Mol Struct， 2025， 1322： 140350.
19	陈凯锋，刘赟，沈志豪，等. 空间位阻对氢键构筑的嵌段共聚物微相分离结构的影响［J］. 高分子学报， 2023， 54（11）： 1681-1696.
	CHEN K F， LIU B， SHEN Z H， et al. Effect of steric hindrance on the microphase separation structure of block copolymers constructed by hydrogen bonds［J］. Acta Polym Sin， 2023， 54（11）： 1681-1696.
20	OVSYANNIKOV A S， LANG M N， FERLAY S， et al. Molecular tectonics： tetracarboxythiacalix ［4］ arene derivatives as tectons for the formation of hydrogen-bonded networks［J］. CrystEngComm， 2016， 18（44）： 8622-8630.
21	种丹丹，张洁，宛新华. 多酸-有机聚合物超分子自组装杂化材料［J］. 高分子学报， 2022， 27（8）： 56-68.
	ZHONG D D， ZHANG J， WAN X H. Polyacid-organic polymer supramolecular self-assembly of hybrid materials［J］. Acta Polym Sin， 2022， 27（8）： 56-68.
22	孔翔飞，李俊，俞建文，等. 氢键组装的超分子液晶的研究进展［J］. 液晶与显示， 2019， 34（11）： 1037-1054.
	KONG X F， LI J， YU J W， et al. Progress on supramolecular liquid crystals assembled by hydrogen bonds ［J］. Chin J Liq Cryst Disp， 2019， 34（11）： 1037-1054.
23	GU Q， XIA Y， CHEN S， et al. Infrared spectroscopy of gas phase alpha hydroxy carboxylic acid homo and hetero dimers［J］. Phys Chem Chem Phys， 2018， 20（47）： 29601-29609.
24	XIAO Z， YANG W， YAN F， et al. Assembly of calix ［4］ arene carboxylic acid derivatives by hydrogen bonding［J］. CrystEngComm， 2019， 21（3）： 439-448.
25	MOURER M， BOUIZI Y， LECLERC S， et al. Synthesis of a tube-like tetra-bipyridyl， tetra-ethylacetato-calix ［4］ arene in 1，3-alternate conformation and the unexpected crystal structure of its ［bpy（CoCl₂）］₃-［bpy （CoCl₂）（H₂O）］ complex［J］. New J Chem， 2024， 48（35）： 15577-15589.
26	吴唯，陈玉洁，王佳伟，等. 多重氢键网络结构超分子聚合物的合成与性能［J］. 功能高分子学报， 2011， 24（4）： 411-415.
	WU W， CHEN Y J， WANG J W， et al. Synthesis and properties of structured supramolecular polymers of multiple hydrogen-bond networks ［J］. J Funct Polym， 2011， 24（4）： 411-415.
27	ÖZKINALI S. Spectroscopic and thermal properties of newly mixed azocalix ［4］ arene ester derivatives［J］. Dyes Pigm， 2014， 107： 81-89.
28	PODYACHEV S N， GIMAZETDINOVA G S， GUBAIDULLIN A T， et al. Synthesis， structure and coordination properties of novel bifunctional carboxylic derivatives of 1，3-alternate tetrathiacalix ［4］ arene［J］. RSC Adv， 2016， 6（23）： 19531-19544.
29	LOTFI B， TARLANI A， AKBARI-MOGHADDAM P， et al. Multivalent calix ［4］ arene-based fluorescent sensor for detecting silver ions in aqueous media and physiological environment［J］. Biosens Bioelectron， 2017， 90： 290-297.
30	AL-HAZMY S M， AL-HARBY J， HASSAN M， et al. A study of the electronic absorption and emission spectra of DBDMA dye： solvent effect， energy transfer， and fluorescence quenching［J］. J Spectrosc， 2023， 2023（1）： 7802548.
31	TANG F， HUANG Z， XUE J， et al. D-A-D′-type fluorescence dyes with DSE and AIE properties and their sensing applications［J］. J Mol Struct， 2025， 1329（5）： 141432-141441.
32	XIAO Z， YANG W， LUO J， et al. Weak intermolecular interaction directed assembly of calix ［4］ arene derivatives［J］. Cryst Eng Comm， 2019， 21（46）： 7114-7122.
33	张璐璐，王媛媛，朱贵楠，等. 含不同烷基链四苯基丁二烯衍生物的聚集诱导发光及力致变色性能［J］. 化学学报， 2022， 80（3）： 282.
	ZHANG L L， WANG Y Y， ZHU G N， et al. Aggregation-induced luminescence and enchromochromic properties of tetraphenylbutadiene derivatives containing different alkyl chains［J］. Acta Chim， 2022， 80（3）： 282.
34	BOUTAR M， DESROCHES C， MATTOUSSI N， et al. Coordination polymers of zinc （Ⅱ） and manganese （Ⅱ） made by complexation of calix ［4］ arene functionalized with carboxylates afford alveolar materials［J］. Inorg Chim Acta， 2019， 486： 562-567.
35	张照明，赵骏，颜徐州. 协同的共价-超分子聚合物［J］. 高分子学报， 2023， 53（7）： 691-706.
	ZHANG Z M， ZHAO J， YAN X Z. Cooperative production of covalent-supramolecular polymers［J］. Acta Polym Sin， 2023， 53（7）： 691-706.
36	ÖZKINALI S， KOCAOKUT H. Synthesis， spectral characterisation and thermal behaviours of some new p-tert-butylcalix ［4］ arene and calix ［4］ arene-esters containing acryloyl groups［J］. J Mol Struct， 2013， 1031： 70-78.
37	LAKOURAJ M M， TASHAKKORIAN H. Synthesis and investigation of transition metal removing of novel thermally stable polyamides bearing calix ［4］ arene in their backbones［J］. J Macromol Sci Part A， 2012， 49（10）： 806-813.
38	SAYIN S， YILMAZ M. Preparation and uranyl ion extraction studies of calix ［4］ arene-based magnetite nanoparticles［J］. Desalination， 2011， 276（1/2/3）： 328-335.

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Preparation of 1，3-Alternate Calix［4］arene Derivatives and Their Hydrogen-Bonding Polymerization

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