1 / 24

A.E.Arbuzov Institute of Organic & Physical Chemistry, Kazan A.M.Butlerov Chemistry Institute of

A.E.Arbuzov Institute of Organic & Physical Chemistry, Kazan A.M.Butlerov Chemistry Institute of Kazan Federal University, Kazan. Supramolecular chemistry of (thia)calix[4]arenes. I.S.Antipin, S.E.Solovieva, I.I.Stoikov, A.I.Konovalov. Lviv, 6-10 September 2010.

hamilton-klein
Download Presentation

A.E.Arbuzov Institute of Organic & Physical Chemistry, Kazan A.M.Butlerov Chemistry Institute of

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  1. A.E.Arbuzov Institute of Organic & Physical Chemistry, Kazan A.M.Butlerov Chemistry Institute of Kazan Federal University, Kazan Supramolecular chemistry of (thia)calix[4]arenes I.S.Antipin, S.E.Solovieva, I.I.Stoikov, A.I.Konovalov Lviv, 6-10 September 2010

  2. VI International symposium “Design and Synthesis of Supramolecular Architectures” September 18-23, 2011 St.Petersbourg Moscow Kazan Novosibirsk V International symposium “Design and Synthesis of Supramolecular Architectures” 12-16 October 2009 http://iopc.ru/butlerov/Index-e.html

  3. Basic principle of supramolecular chemistry Macrocycles– molecular platform for multipoint interactions realization and multivalent ligands design. Jonathan Swift

  4. Macrocyclic platforms Cyclodextrins Cucurbiturils Calixarenes

  5. CPK-Model Calyx S S S S X X X X X X X X H H H H H H H H Calixarenes X=O, S, NH

  6. H H H H H O O O O O O O O O O O O O O O O H H H H H H H H H H H 1997 –S.Miyanoet al Calix[4]arenes Thiacalix[4]arene V≈10A3 • The characteristic advantages of calix[4]arenes for the constructing of receptors are followed: • the low cost and accessibility of parent macrocycles by one-pot synthesis; • calixarenes can incorporate the small hydrophobic organic molecules into their molecular cavities with the formation of the stable host-guest complexes; • the existence of variety of calixarene conformations: cone, partial cone, 1,2-alternate, 1,3-alternate etc.; • calix[4]arene conformations are rather rigid and are able to fix the required spatial orientation of binding centers; • nontoxicity of calixarene platforms. • calixarene platform gives an unique possibility to decorate the upper and lower rim of macrocycle by the suitable heteroatom groups and to form the molecular system possessing the several binding centers; Cone Partial Cone 1,3-Alternate 1,2-Alternate

  7. S S S S O H O H O H O H Mono, Di, Tri and Tetra Substituted Derivatives Cone Partial Cone 1,3-Alternate 1,2-Alternate R R R R R O O O O O O O O O O O O O O O O R R R R R R R R R R R Background of Calixarene Chemistry Upper Rim Lower Rim Main Problem: Stereo and Regio Selective Functionalization of Lower and Upper Rim

  8. 2 + n n Outline 1. Covalent assembly: towards nanosized molecules “guest hν quenching 2. Noncovalent assembly: towards “soft” nanosystems Functions Receptor - signal Phototransforming – accumalation

  9. Z Y O O O N N R R N R n + M R R N N N R O O O Y Z Clathrochelates – tris-dioximates Y= B, Ge, Sn, Sb, Mn+= Fe2+, Co2+, Co1+, Ru2+ R = Hal, Ar, Alk, XAr, XAlk, Z=F, Alk, Ph • The characteristic advantages of macrobicyclic tris-dioximates: • accessibility by one or two-step synthesis; • stability in acidic and alkaline media; • metal ability to redox processes inside of the ligand cavity; • the possibility of side and apical position functionalization.

  10. S O S S S S Cl S S S S Cl O O S O SH SH n n n n n + + + + + M M M M M O O S HS S SH Cl S S S S O O Guest Guest S S S S O O HS SH Cl S S O O Design of new types of cavitands: conjugates of clathrochelate and thiacalixarenes Route a 1,3-Alternate Route b Cone

  11. Where we are going?

  12. S ( C H ) n O 2 SH S HS ( C H ) n 2 O HS ( C H ) n O 2 S SH ( C H ) n O 2 S Synthesis calixarene/clathrochelate conjugates: effect of methylene spacer length F B O O O Cl N N N 2+ Fe Cl N N N + O O O B F n=3, 4, 5 F S F B ( C H ) n O B 2 O O O O S O O S S ( C H ) n N N N N N 2 N O 2+ 2+ Fe Fe Yield: n=3:0% n=4:58% n=5: 2% S ( C H ) n O N 2 N N N N N S O S O O O O ( C H ) n O O B 2 B S F F

  13. Synthesis calixarene/clathrochelate conjugates: effect of methylene spacer length N=3, Yield 20% O O B O N N C l N F e F N N N S S B O O O O O O O B S N N N O F S F N=5, Yield 65% F e O O O B N S N N O S O N N N C l O O B O S F e F S N N N O O O B

  14. R R O R O O O O O S S S S S S S S S S S S O O O O O O O O O O O O O O R R R R O R R O O O R R R 5 N O R = 6 R = N Noncovalent assembly of nanoaggregates Cone Paco 1,3-Alternate 15

  15. O H N O S S S S O O O O N H H N H N O O Nanoparticles size distribution of Ag complexin CH2Cl2 3 hours + Ag+ 28 hours Paco-7 16

  16. 17 H C C H 2 2 N H H N O O C C O O S S S S O O O C C O N H H N H C C H 2 2 SEM nanoparticles image of Ag(I) complex in CH2Cl2 1,3-alt - 10

  17. The size of the aggregates formed thiacalix[4]arenes, functionalized with hydrazide groups, with metal cations

  18. Photo-switching of thiacalix[4]arene derivative 1 containing azobenzene moieties UV spectra (5•10–6 mol L–1, 1cm cell) of p-tert butylthiacalix[4]arene in the trans (1)and cis (2)formsin dichloromethane

  19. Photo-switchable self-assembly of nanosized aggregates

  20. Model of photo-switchable self-assembly: first step from the inanimate to living matter hν (254 nm)

  21. Commercial contrast agents Magnetic Resonance Imaging (MRI) RelaxivityR1p~ 3000-5000 M-1s-1, lgβ ~ 19-26 • Main approaches to relaxivity enhancement: • the induction of steric hindrance around the water binding site; • the rise of the complex molecular mass due to aggregation.

  22. paco cone 1,3-alt Effect of macrocycleconformation on Gd(III) relaxivity TC[4] Ac

  23. Acknowledgment Academician A.I.Konovalov Scientific teamin KFU Prof. I.I.Stoikov Dr.O.A.Mostovaya A.Yu.Zhykov E.A.Yushkova E.A. Zaikov Collaborators Prof. Ya.Z.Voloshin Prof. M.W.Hosseini Prof. R.R.Amirov Prof. A.R.Mustafina Prof. G.A.Evtyugin Dr. E.E.Stoikova Dr. A.T.Gubaidullin Scientific team in IOPC Dr. S.E.Solovieva Dr. E.A.Popova Dr. S.R.Kleshnina Dr. M.N.Kozlova Dr.A.A.Tuyftin Grants Russian Foundation for Basic Research Russian Academy of Sciences Ministry of Education and Sciences RF CRDF

More Related