Embed Size (px)
DESCRIPTION
M.A.(Tony)Whitehead Chemistry Departmen t McGill. Molecular Orbital Modelling of Dendrimers & Nano-Tubes. REVIEW OF TALKS GIVEN AT:. Friday, 28 th .August, 2008 FAPPMS 2008, Three Rivers Quebec. Saturday27th. June,2009 ACA 2009,Montreal, Quebec. Monday 15 th . June,2009 - PowerPoint PPT Presentation
Citation preview
M.A.(Tony)Whitehead
Chemistry Department
McGill
Molecular Orbital Modelling of Dendrimers & Nano-Tubes
Monday 15th. June,2009HPCS 2009 - Kingston, Ontario
Friday, 28th.August, 2008FAPPMS 2008, Three RiversQuebec
REVIEW OF TALKS GIVEN AT:
Saturday27th. June,2009ACA 2009,Montreal, Quebec
DRENDRITIC MOLECULES
Dr Ashok Kakkar
Ye Tien
Rami Hourani
OOSi
OOH
OH
SiO
OH
HO
OSi
O
OHHO
Me
MeMe
Me
MeMe
OOSi
OO
OSi
SiO
O
SiO
O
O
Si
Si
O
O
OH
OH
OH
HOOH
HO
HO
HO
OSi
O
OOSiSi
OO
OH
OH
OH
Me
Me
MeMe
MeMe
Me
MeMe
MeMe
Me
Me
Me Me
Me
MeMe
HO
OOSi
OO
OSi
SiO
O
SiO
O
O
Si
Si
O
O
O Si
O Si
O
OSi
SiO
O
O
O
O
OSi
Si
O
O
O
O
Si
Si
O
O
HO
OH
OH
OH
OH
HO
OHHOOHHO
HO
HO
HO
HO
HO
HO
OSi
O
OOSiSi
OO
O
O
O
OSiO
SiO
Si O
SiO
HO
HO
OHHO OHHO
OH
OH
MeMe
Me
Me
MeMe
Me
Me
Me
Me
Me
Me
MeMe
Me
MeMe
Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMe
MeMe
Me
MeMe
MeMe
Me
Me
Me Me
Me
MeMe
OOSi
OSi
OSi
O
OOSiSi
O
Me
MeMe
Me
Me
Me Me
Me
MeMe
O
O
SiO
SiO
OO
O
O
SiO
SiO
SiO
Si O
HO OHHO
OH
HO
OH
OH
OH
O
O
O
SiO
SiO
OO
O
O
SiO
SiO
SiO
SiO
OHHOOH
HO
OH
HO
HO
HO
O Si O
O SiO
O
O
Si O
SiO
OH
OH
OH
OH
O SiO
O
O
Si O
Si O
OH
OH
OH
OH
OSi
O
OSi O
O
O
SiO
SiO
OH
OH
OH
OH
OSi
O
O OSi
OSiO
OH HOOH
O
OSiO
OSiO
O
O
SiO
SiO
HO
HO
HO
HO
OSiO
O
O
SiO
SiO
HO
HO
HO
HO
OSi
O
OSiO
O
O
SiO
SiO
HO
HO
HO
OH
OSiO
OOSiO
SiO
HOOHHO
OH HO
Me
Me
Me
Me
Me MeMeMe
Me
MeMe
Me
Me
MeMe
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMeMe
Me
Me
Me Me
MeMeMeMeMeMeMeMe
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMe
MeMe MeMe Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMe
Me MeMe
Me
Me
OOSi
OSi
OSi
O
OOSiSi
O
Me
MeMe
Me
Me
Me Me
Me
MeMe
O
O
SiO
SiO
OO
O
O
SiO
SiO
SiO
Si O
O OO
O
O
O
O
O
O
O
O
SiO
SiO
OO
O
O
SiO
SiO
SiO
SiO
OO
O
O
O
O Si O
O SiO
O
O
Si O
SiO
O
O
O
O SiO
O
O
Si O
Si O
O
O
O
O
OSi
O
OSi O
O
O
SiO
SiO
O
O
O
O
OSi
O
O OSi
OSiO
O OO
O
OSiO
OSiO
O
O
SiO
SiO
O
OSiO
O
O
SiO
SiO
O
OOSi
O
OSiO
O
O
SiO
SiO
O
OSiO
OOSiO
SiO
OO
O O
Me
Me
Me
Me
Me MeMeMe
Me
MeMe
Me
Me
MeMe
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMeMe
Me
Me
Me Me
MeMeMeMeMeMeMeMe
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMe
MeMe MeMe Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMe
Me MeMeMe
Me
SiO
OH
Si O
SiSi
O
O
OHOH
OH
OH
OHOH
SiO
Si O
OH
OH
OH
OH
SiO
SiO
OH
OH
OH
O
O
O
SiO
HO
SiO
SiSi
O
O
HOHO
HO
HO
HOHO
SiO
SiO
HO
HO
HO
HO
SiO
SiO
HO
HO
HO
HO
OH OH
SiO
SiO
SiO
SiO
Si O
OO SiO
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
SiO
SiO
Si O
Si
O
Si OSi
O
Si OSiOSi
OSi
O
OH OH OH OHOH
OH
OHOH
OH
OHOH
OH
OH
OH
OH
OH
OH
OH
OHOH
O
O
O
O
O
O
O
O
SiO
SiO
SiO
SiO
SiO
SiO
HO
HO
HO
HO
HO
HO
HO
HO
HO
HO
HO
HO
SiO
SiO
SiO
Si
O
SiOSi
O
SiO SiO Si
OSi
O
HOHOHOHOHO
HO
HO
HOHO
HOHO
HO
HO
HO
HO
HO
HO
HO
HO OH
OH
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2Me2 Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2Me2
Me2Me2Me2
Me2
Me2
Me2Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Me2
Divergent Synthesis of DHBA-Based Dendrimers
Bourrier O., Kakkar A. K., J. Mater. Chem. 2003, 13, 1306
OHHO
HO
(DHBA)
DHBA
Me2Si(NMe2)2
3,5-dihydroxybenzyl alcohol
Aggregate at cac
Hourani R., Kakkar A., Whitehead M. A., J. Mater. Chem., 2005, 15, 2106–2113
Higher generation number… more globular structures giving well defined internal cavities
PM3 optimised structures: DHBA-Based Dendrimers
TOP VIEW
SIDE VIEW
DLMO are orthogonal to all other DLMO and independentDG 1
DG 2 DLMO are the same as DG1 in shape and energy:
Encapsulation of DR1 in DHBA-Based Dendrimers
Aggregation & Encapsulation
.
OOSi O
O
O Si
SiO
O
SiO
O
O
Si
Si
O
O
O Si
O Si
O
OSi
SiO
O
O
O
O
OSi
Si
O
O
O
O
Si
Si
O
O
HO
OH
OH
OH
OH
HO
OHHOOHHO
HO
HO
HO
HO
HO
HO
OSi
O
OOSiSi
OO
O
O
O
OSiO
SiO
Si O
SiO
HO
HO
OHHO OHHO
OH
OH
MeMe
Me
Me
MeMe
Me
Me
Me
Me
Me
Me
MeMe
Me
MeMe
Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMe
MeMe
Me
MeMe
MeMe
Me
Me
Me Me
Me
MeMe
OOSi O
O
O Si
SiO
O
SiO
O
O
Si
Si
O
O
O Si
O Si
O
OSi
SiO
O
O
O
O
OSi
Si
O
O
O
O
Si
Si
O
O
HO
OH
OH
OH
OH
HO
OHHOOHHO
HO
HO
HO
HO
HO
HO
OSi
O
OOSiSi
OO
O
O
O
OSiO
SiO
Si O
SiO
HO
HO
OHHO OHHO
OH
OH
MeMe
Me
Me
MeMe
Me
Me
Me
Me
Me
Me
MeMe
Me
MeMe
Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMe
MeMe
Me
MeMe
MeMe
Me
Me
Me Me
Me
MeMe
OOSi O
O
O Si
SiO
O
SiO
O
O
Si
Si
O
O
O Si
O Si
O
OSi
SiO
O
O
O
O
OSi
Si
O
O
O
O
Si
Si
O
O
HO
OH
OH
OH
OH
HO
OHHOOHHO
HO
HO
HO
HO
HO
HO
OSi
O
OOSiSi
OO
O
O
O
OSiO
SiO
Si O
SiO
HO
HO
OHHO OHHO
OH
OH
MeMe
Me
Me
MeMe
Me
Me
Me
Me
Me
Me
MeMe
Me
MeMe
Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMe
MeMe
Me
MeMe
MeMe
Me
Me
Me Me
Me
MeMe
OOSi
OO
O Si
SiO
O
SiO
O
O
Si
Si
O
O
O Si
O Si
O
OSi
SiO
O
O
O
O
OSi
Si
O
O
O
O
Si
Si
O
O
HO
OH
OH
OH
OH
HO
OHHOOHHO
HO
HO
HO
HO
HO
HO
OSi
O
OOSiSi
OO
O
O
O
OSiO
SiO
Si O
SiO
HO
HO
OHHO OHHO
OH
OH
MeMe
Me
Me
MeMe
Me
Me
Me
Me
Me
Me
MeMe
Me
MeMe
Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMe
MeMe
Me
MeMe
MeMe
Me
Me
Me Me
Me
MeMe
OOSi O
O
O Si
SiO
O
SiO
O
O
Si
Si
O
O
O Si
O Si
O
OSi
SiO
O
O
O
O
OSi
Si
O
O
O
O
Si
Si
O
O
HO
OH
OH
OH
OH
HO
OHHOOHHO
HO
HO
HO
HO
HO
HO
OSi
O
OOSiSi
OO
O
O
O
OSiO
SiO
Si O
SiO
HO
HO
OHHO OHHO
OH
OH
MeMe
Me
Me
MeMe
Me
Me
Me
Me
Me
Me
MeMe
Me
MeMe
Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMe
MeMe
Me
MeMe
MeMe
Me
Me
Me Me
Me
MeMe
OOSi
OO
O Si
SiO
O
SiO
O
O
Si
Si
O
O
O Si
O Si
O
OSi
SiO
O
O
O
O
OSi
Si
O
O
O
O
Si
Si
O
O
HO
OH
OH
OH
OH
HO
OHHOOHHO
HO
HO
HO
HO
HO
HO
OSi
O
OOSiSi
OO
O
O
O
OSiO
SiO
Si O
SiO
HO
HO
OHHO OHHO
OH
OH
MeMe
Me
Me
MeMe
Me
Me
Me
Me
Me
Me
MeMe
Me
MeMe
Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMe
MeMe
Me
MeMe
MeMe
Me
Me
Me Me
Me
MeMe
OOSi O
O
O Si
SiO
O
SiO
O
O
Si
Si
O
O
O Si
O Si
O
OSi
SiO
O
O
O
O
OSi
Si
O
O
O
O
Si
Si
O
O
HO
OH
OH
OH
OH
HO
OHHOOHHO
HO
HO
HO
HO
HO
HO
OSi
O
OOSiSi
OO
O
O
O
OSiO
SiO
Si O
SiO
HO
HO
OHHO OHHO
OH
OH
MeMe
Me
Me
MeMe
Me
Me
Me
Me
Me
Me
MeMe
Me
MeMe
Me
Me
Me
Me
Me
Me
Me
Me
Me
MeMe
MeMe
Me
MeMe
MeMe
Me
Me
Me Me
Me
MeMe
NN
NO2
N
=
OH
(DR1)
Disperse Red 1
Blue Shift in λmax of DR1
0
0.5
1
1.5
2
2.5
300 400 500 600 700 800Wavelength (nm)
DG4+DR1
Free DR1
Divergent Synthesis: TEB-Based Dendrimers
Sn Sn
Sn
Sn Sn
Sn
Sn
Sn
SnSn
Sn
Sn
Sn Sn
Sn
Sn
Sn
Sn
Sn
Sn
Sn
SnSn
Sn
Sn
Sn
Sn
SnSn
Sn
Sn
Sn
Sn
Me2Sn(NEt2)2
1,3,5 Triethynylbenzene
(TEB)
(TEB)
Hourani R., Whitehead M. A., and Kakkar A., Macromolecules, 2008, 41, 508.
1,3,5 Tri Ethynyl Benzene
Structures of TEB-Based Dendrimers
Development of turbine-like structure
TOP VIEW
SIDE VIEW
1,3,5 Tri Ethynyl Benzene
Organometallic Dendrimers by Direct Replacement
An easy route to include transition metal centres in the dendrimers
Lewis J. et al, J. Organomet. Chem., 1992, 425, 165.
Sn R Sn R M
PR3
PR3
n
ClPtClPR3
PR3
Pt Pt
PtPR3R3P
R3P
PR3 R3P
PR3
Sn Sn
Sn
30%
No Catalyst!
M = Pd, Pt...
ClMCl
PR3
PR3
ClPtClPR3
PR3
Pt Pt
PtPR3R3P
R3P
PR3 R3P
PR3
Sn Sn
Sn
30%
No Catalyst!
DHBA
TEB
DG1
PLATINUM
N3
Si
Si
N
N
N
NN
N
Si
Si
Si
Si
N
NN
Si
SiSodium Ascorbate
CuSO4
3.3 eq.
Using “Click” Chemistry To Build Dendrimers
1,3,5 Tri Ethynyl Benzene
TEB
N
N
N
NN
N
Si
Si
Si
Si
N
NN
Si
Si
N
N
N
NN
N
N
NN
Using “Click” Chemistry To Build Dendrimers
Remove the silyl groups
Then continue to build from the triple bonds
DG 1DG 2
Same DLMO shape
-0.205 au. lumo +2
-0.018au lumo+8
-0.016 au lumo+12
-0.314 au homo
-0.022au lumo
Centre: -0.317a.u. homo-1 Left: -0.331a.u homo-4 Right: -0.325a.u. homo-2 Bottom: -0.326a.u. homo-3
SMI NANO TUBESDr.Theo van de Ven
Tom Lazzara
600 Lower π-π stabilization, higher maleimide chain interactions
CONCLUSIONSCONCLUSIONS
Using insight and care and understanding the weaknessesUsing insight and care and understanding the weaknessesOf the theories and programmesOf the theories and programmes
1. Theory gave insight into dendrimer structures1. Theory gave insight into dendrimer structures
2. Theory predicted possible metal containing dendrimers2. Theory predicted possible metal containing dendrimers
3. Theory predicted nano-structures which were made3. Theory predicted nano-structures which were made
4. Theory helped to analyse the problems of4. Theory helped to analyse the problems of
SMI nano- structures and led to synthetic methodsSMI nano- structures and led to synthetic methods
END
WATER ON CALCITE AND ARAGONITE
Water on Calcitebreaks the Ca-O bond
Joseph Kinghorn-Taenzer
Intakhab Alam Zeeshan
ARAGONITE
CRYSTAL
DOUBLE LAYER
SINGLE LAYER ATOMS FIXED
CUT
CUT
Side view
SIDE TOP
2H2O SIDE2H2O SIDE
4H2O SIDE 4H2O TOP
SIDE
TOP
2H2O SIDE and TOP pictures show 1) no bonds broken in the Aragonite Double Layer 2H2O lean closer to the surface
4H2O SIDE and TOP (1) and (2) Pictures show no bonds broken in the AragoniteDouble Layer 4H2O arrange their H atoms to avoid each other
-1.045 HOMO +152
O…H = 1.067Å
H-bond = 2.489Å
H-bond
Average Valence Bond H-bond distance = 1.97Å
-1.085au HOMO +118 O..H=1.53Å9; H-bond=2.578Å
-1.054 au HOMO+146O..H = 1.005Å; H-bond=2.579Å
-1.086au HOMO +117O..H=1.068Å; H-bond=2.429Å
-1.088au HOMO + 116O..H=0.977Å; H-bond=2.986Å
-1.091au HOMO+115O..H=1.005Å; H-bond=2.577Å
-0.614au HOMO+289 O..H 1 =0.986Å; H-bond=2.731Å
DOUBLE LAYER: FOUR H2O Both water H (H1,H2) are bonded to different Osurface
-0.617au HOMO+288O..H 2 =0.982Å; H-bond=3.79Å
rotate to show H-bond
H1
H2
rotate to show H-bond
-0.676au HOMO+268
LEFT O..H=1.027Å; H-bond=2.453Å
RIGHT O..H=1.052Å; H-bond=2.395Å
Both Hydrogen Bonds at theend CaO are in thesame DLMO 268
CONCLUSIONS
1)Prediction of 3D structures of organic and Sn and Pt dendrimers
2)Prediction of the form of nano tubes from SMI
3)Prediction that unlike calcite which dissolves in Water,
Aragonite forms weak H-bonds and does not dissolve.
THEORETICAL METHODS FOR CALCULATIONS
1 Molecular Mechanics: Balls and Springs
2 Quantum Mechanics
3 Molecular Dynamics
Newtonian Dynamics
2a Density Functional theory; n3
n4 catastropheNeglect of DiatomicDifferential Overlap n3
PM3 Large parameter space
Research Supported:The NSERC (CANADA): Discovery GrantSummer Undergrad Research Student 2008: Intakhab Alam Zeeshan
Le Fonds québécois de la recherche sur la nature et les technologies.Doctoral Scholarships:Tom Lazzara, 2007 Rami Hourani, 2007
Centre for Self-Assembled Chemical Structures:Summer Undergrad Research Award, 2008
Ye Tian:
SIGMA XI: Grant in Aid of Research: Tom Lazzara, 2007 Rami Hourani, 2007
!["Deleuze's Encounter With Whitehead" [Chapter 2 of Whitehead book]](https://img.pdfslide.us/doc/110x75/589d92621a28ab494a8bb804/deleuzes-encounter-with-whitehead-chapter-2-of-whitehead-book.jpg)
