Oxacalix[n](het)arenes

Maes, Wouter; Dehaen, Wim

doi:10.1039/b718356a

Cited by 241 publications

(119 citation statements)

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“…[8,9] Within one of our research groups, we have been studying the synthesis and reactivity of 4,6-dichloropyrimidines as versatile structural building blocks for meso-pyrimidinylsubstituted porphyrins, [10] heteracalix [m]arene [m]pyrimidines, [11] and pyrimidine-based (porphyrin) dendrimers. [12,13] During the course of our studies on pyrimidinylporphyrins, it was discovered that a slight modification of the reaction conditions, as optimized for porphyrins, results in the formation of either expanded (penta-and hexaphyrins) [14] or contracted [15] porphyrin analogues. The major advantage concerning the introduction of dichloropyrimidinyl moieties on the meso positions of a porphyrinoid macrocycle is the wide scope of functionalization reactions that can be performed on the dichloropyrimidine units.…”

Section: Introductionmentioning

confidence: 99%

Synthetic, Structural, and Photophysical Exploration of meso‐Pyrimidinyl‐Substituted AB₂‐Corroles

Ngo

Puntoriero²,

Nastasi³

et al. 2010

Chemistry A European J

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meso-Pyrimidinyl-substituted AB(2)-corroles were efficiently synthesized starting from 5-mesityldipyrromethane and various 2-substituted 4,6-dichloropyrimidine-5-carbaldehydes. The corrole yield was significantly enhanced by optimization of the amount of Lewis acid catalyst (BF(3).OEt(2)). The main advantage of pyrimidinylcorroles over other meso-triarylcorroles is their wide range of functionalization possibilities, which has been explored by nucleophilic and electrophilic aromatic substitution, and Pd-catalyzed cross-coupling reactions. Stepwise substitution of the chlorine functions afforded asymmetrically substituted pyrimidinylcorroles. Due to the lability of the free-base corrole macrocycles, functionalization of the corrole periphery was preferentially performed on the Cu-metalated counterparts. Functionalized free-base AB(2)-pyrimidinylcorroles were, however, readily accessible by the reversible sequence Cu insertion and subsequent reductive demetalation. AB(2)-pyrimidinylcorroles can hence be regarded as highly versatile platforms towards more sophisticated corrole systems. X-ray analysis of a bis(4-tert-butylphenoxy)-substituted Cu-pyrimidinylcorrole showed the typical features of a Cu-corrole: short N-Cu distances and a saddled corrole plane. The absorption spectra and photophysical properties of some representative free-base AB(2)-pyrimidinylcorroles were examined in depth. The absorption spectra displayed typical corrole features: intense spin-allowed pi-pi* bands, which can be classified as Soret- and Q-type bands. The photophysical properties, investigated both in fluid solution at room temperature and in rigid matrix at 77 K, were governed by the lowest-lying pi-pi* singlet state; however, in most cases, a state with partial charge-transfer character (from the corrole ring to the pyrimidinyl group) was proposed to contribute to the dynamic properties of the emissive level.

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Section: Introductionmentioning

confidence: 99%

Synthetic, Structural, and Photophysical Exploration of meso‐Pyrimidinyl‐Substituted AB₂‐Corroles

Ngo

Puntoriero²,

Nastasi³

et al. 2010

Chemistry A European J

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“…杂杯芳烃领域目前一个重要的研究内容就是改善其空腔尺寸和空穴特性从而提升其超分子性能, 以往的研究工作主要是通过增加杯芳烃的构筑单元来调控空腔大小, 如杂杯 [4], [6], [8]芳烃等. 近年来, 我们小组提出了另一种策略来改变杂杯芳烃的空腔大小和特性, 即运用刚性大尺寸的构筑单元-三蝶烯…”

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“…我们通过 2,7-二羟基三蝶烯与 2,3,5,6-四氯吡啶、1,5-二氟-2,4-二硝基苯和三聚氰氯的 S N Ar 反应, 构筑了一系列基于三蝶烯的扩展氧杂杯 [4] 芳烃化合物 [7a] . 通过 NMR、MS 和 X-射线晶体等手段证实每一个反应都生成了一对互为顺反异构体的大环化合物, 其中, 顺式大环在固态下都以船式构象存在, 而不同的反式大环在常温下则有椅式和扭曲船式两种构象.…”

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“…对其固态组装的研究还表明扩展的氧杂杯芳烃能够在固态下形成有机管状结构以及多孔状高级超分子组装体, 并且在此组装过程中, C-Cl…Cl, C-Cl…O 和 C-Cl…π 等多重氯键起着重要的作用. 我们利用 2,7-二氨基三蝶烯片断与三聚氰氯、1,5-二氟-2,4-二硝基苯或 2,6-二氯-3,5-二氰基吡啶的 S N Ar 反应, 构筑了一系列三蝶烯衍生的 N-H 桥连的氮杂杯 [4] 1, 53.3, 53.8, 116.6, 117.6, 120.9, 121.9, 123.5, 123.8, 124.7, 125.7, 134.8, 136.4, 140.7, 142.2, 145.2, 145.6, 146.7, 150.6, 155.5, 157.7 H 3.44, N 13.65; found C 79.22, H 3.51, N 13.47. …”

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Synthesis and Structures of Triptycene-derived Diazadioxacalixarenes

Xue¹,

Hu²,

Chen³

2012

Acta Chim. Sinica

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A series of triptycene-derived diazadioxacalixarenes were synthesized by two-step S N Ar reactions from 2,7-diaminotriptycene, 2,7-dihydroxytriptycene with heterocyclic compounds such as cyanuric chloride, 1,5-difluoro-2,4-dinitrobenzene and 2,6-dichloropyridine-3,5-dicarbonitrile, respectively. X-Ray crystallographic analysis of the trimer obtained by reaction of 2,7-diaminotriptycene with 2,6-dichloropyridine-3,5-dicarbonitrile showed that the two pyridine rings are in the same side of the triptycene unit and the two residual chloride atoms point to the same direction, which greatly favors the subsequent cyclization reactions with 2,7-dihydroxytriptycene. Due to the 3D characteristic of triptycene unit, the synthetic macrocyclic molecules are pairs of diastereomers. Their structures and self-assembled properties were studied by NMR spectra and X-ray crystallographic analysis. The results showed that the diazadioxacalixarenes have some different properties from those of tetraazacalixarenes and tetraoxacalixarenes. The triptycene-derived tetra-NH-bridged azacalixarenes obtained from the reaction of 2,7-diaminotriptycene with 2,6-dichloropyridine-3,5-dicarbonitrile can self-assemble into a large square-shaped organic nanotube with aromatic single-walled surfaces by four infinite one-dimensional H-bond chains, and the nanotubes could further assemble into a 3D honeycombed architecture. However, the diazadioxacalixarene analog could not self-assemble into such architecture due to the structural and conformational changes made by the displacement of two bridging nitrogen atoms with oxygen atoms, which led to the destroy of the H-bond chains formed from the bridging NH groups with the cyano groups. Our results also showed that the trimer of 2,7-diaminotriptycene and 2,6-dichloropyridine-3,5-dicarbonitrile could self-assemble into a nanotube architecture with a hole diameter of 8.16 Å×8.95 Å through C-H… Cl H-bond (d H … Cl ＝2.87 Å, θ C -H … Cl ＝149.31°), π…π (d π … π ＝3.67 Å) stacking and C-H…π (d C -H … π ＝2.86 Å) interactions.

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“…Pillarenes, [62][63][64] in which benzene rings are linked by para, and not by meta positions as in calixarenes should also be included. A special group are the thia, oxa and azacalixarenes, in which the linking methylene groups of calixarenes are formally replaced by sulfur, [65][66][67] oxygen, [68][69][70] or nitrogen, [71][72][73] atoms, respectively.…”

Section: Introductionmentioning

confidence: 99%

Functionalization reactions of calixarenes

Śliwa¹,

Deska²

2011

Arkivoc

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Oxacalix[n](het)arenes

Cited by 241 publications

References 40 publications

Synthetic, Structural, and Photophysical Exploration of meso‐Pyrimidinyl‐Substituted AB₂‐Corroles

Synthetic, Structural, and Photophysical Exploration of meso‐Pyrimidinyl‐Substituted AB₂‐Corroles

Synthesis and Structures of Triptycene-derived Diazadioxacalixarenes

Functionalization reactions of calixarenes

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Oxacalix[n](het)arenes

Cited by 241 publications

References 40 publications

Synthetic, Structural, and Photophysical Exploration of meso‐Pyrimidinyl‐Substituted AB2‐Corroles

Synthetic, Structural, and Photophysical Exploration of meso‐Pyrimidinyl‐Substituted AB2‐Corroles

Synthesis and Structures of Triptycene-derived Diazadioxacalixarenes

Functionalization reactions of calixarenes

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Synthetic, Structural, and Photophysical Exploration of meso‐Pyrimidinyl‐Substituted AB₂‐Corroles

Synthetic, Structural, and Photophysical Exploration of meso‐Pyrimidinyl‐Substituted AB₂‐Corroles