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Phthalocyanines:
From Molecular Structures to Solid-state Arrangements
Dr. Michael Klaus ENGEL ([email protected])
Dainippon Ink & Chemicals, Inc.Central Research Laboratories; Sakura-shi, Japan
Classification of Phthalocyanine Molecular Structures
Arrangement of the Phthalocyanine Units in Solid-state
Start: Basic information about Phthalocyanine Molecular Structures
Phthalocyanines
Molecular properties Solid-state properties PcCu -PcCu is greenish blue -PcCu is reddish blueStructure-Property Relationships
ICPP-3, New Orleans, July 12, 2004
Molecular Structures: BasicsX=CH: Tetrabenzoporphyrin: TBPH2
1) 139.0 pm 2) 249.5 pm; 127.9°3) 295.5 pm4) 688.6 pm
X=N: Phthalocyanine: PcCo1) 131.7 pm2) 229.7 pm; 121.5° 3) 269.8 pm 4) 670.5 pm
Most of the metallic elements and semimetals can be coordinated in the center of the macrocycle.Molecular structure is influenced by- the size of the central atom M, - the oxidation state of the central atom M.Two kinds of molecular axes:- bridging-nitrogen molecular axis (Nbr)- isoindole-nitrogen molecular axis (Ni)
N
N
X
N
X
N
X
XM
4
1
23
Nbrmolecularaxis
Nimolecularaxis
ICPP-3, New Orleans, July 12, 2004
Molecular Structures: BasicsCoord.Nr. Oxid.Nr. Geometry Mol.Sym. Expl.
4 2 square planar
D4h PcCu
5 2, 3, 4, 5 square pyramidal
C4vPcSn
PcAlClPcTiOPcReN
6tr 4, 5, 6 octahedral OhPcSiCl2
PcMoOCl
6cis 4 trigonal prismatic
D3hPcNbCl2
7cis 5 capped trigonal prismat
ic
C2v PcNbCl3
8cis/8bis 3, 4 cubic Oh [Pc2La]-
8cis/8bis 3, 4 square antiprismatic
D4d Pc2Zr
NN
NN
NN
NN
X
NN
X
NN
X
N
X
NN
N
X
X
NN
NN
XX
N
NN
N
N
N
N
N
NN
N
N
N
N
ICPP-3, New Orleans, July 12, 2004
Molecular Structures: MonomersMonomeric phthalocyanines with planar macrocycle and identical faces
Monomeric phthalocyanines with bent macrocycle and different faces
CN6cis
CN7cis CN8cis
CN6trCN1 CN4
CN5 CN5
ICPP-3, New Orleans, July 12, 2004
Molecular Structures: Dimers
H
Bis- and trisphthalocyanines with bent macrocycles
Dimeric phthalocyanines with planar or bent macrocycles
CN8bis CN8bis CN8bis
CN6tr
CN6cisCN7cis
CN5 CN5
CN8cis
ICPP-3, New Orleans, July 12, 2004
Increased possibilities of interactions
N
N
N
N
N
N
N
NM
Phthalocyanines additional interactionpossibilities due to the presence of heteroatoms.
Hydrogen atoms electronegative atomsNitrogen atoms hydrogen atoms axial ligands central atomsCentral atoms and axial ligands central atoms axial ligands nitrogen atoms
Aromatic hydrocarbons:Interaction between aromatic macrocycles: interactions and H- interactions
ICPP-3, New Orleans, July 12, 2004
Arrangements: Group CN4 (PcM)
4 Basic overlap geometries
-PcPt -PcH2 -PcCu x1-PcH2
overlap along Nbr molecular axis overlap along Ni molecular axis
intermolecular bonding between Nbr and center stabilizes -polymorphs
the big confusion
ICPP-3, New Orleans, July 12, 2004
Arrangements: Group CN4 (PcM)
Orientation of phthalocyanines in neighboring columns
-PcPt
-PcH2
-PcCu
x1-PcH2
S2 screw axisIntercolumnar hydrogen-bonding
intercolumnar distancesN…H > 3.2 Åmuch weaker bonding
2.7044 Å
2.6465 Å
Herringbone stacking
ICPP-3, New Orleans, July 12, 2004
Arrangements: Group CN4 (PcM)
x1-PcH2
-PcPt -PcH2
-PcCu
-PcPt
x2-PcH2 x1-PcH2
(Nbr)
(Ni)
2.6134 Å3.0143 Å 3.0499 Å
2.8408 Å
ICPP-3, New Orleans, July 12, 2004
Arrangements: Group CN6tr (PcMX2)
x1-PcH2
overlap in CN4
PcSnI2 PcCoCl2 PcSnI2
much smaller in CN6tr
spatial need of axial ligandsIntermol. hydrogen bonding+ repulsive interaction
ICPP-3, New Orleans, July 12, 2004
Arrangements: Group CN6tr (PcMX2)
x1-PcH2
Network structure view along the column axes
Network structure view along the column axes
Intercolumnar hydrogen bonding
-PcGe(OH)2
-PcGe(OH)2 2.592 Å
2.568 Å
Intercolumnar hydrogen bonding
ICPP-3, New Orleans, July 12, 2004
Molecular Structures: Group CN5 (PcMX)
M
Ni
N
Ni
NNi
N
NiN
Ca
Ca
Lax
Ni-MNi-Ctr
MNi Ni CC
= 180o isoindole unit
Why do some phthalocyanines have a saucer-shaped macrocycle ?
convex face
concave face
2 different faces each face leads to a different arrangement
MNi Ni CC
180o
turn around axisthrough C
MNi Ni CC
saucer-shaped
ICPP-3, New Orleans, July 12, 2004
Arrangements: Group CN5 (PcMX)concave convex
sheet-type (or brickstone) arrangementcolumnar (slipped-stacked) arrangements
layer-type arrangements
Ni Nbr no shift
ICPP-3, New Orleans, July 12, 2004
Arrangements: Group CN5 (PcMX)
molecular lego
concavelayer-type convex
+
+
+
PcGaCl
PcAlCl
PcZnCl
Ni
Nbr
no shift
ICPP-3, New Orleans, July 12, 2004
Hydrogen bonding
PcSn
PcNbCl2 PcSnCl2
molecular deformation through hydrogen-bonding
flattening throughrepulsive interaction
parallel not parallel ca. 3.5 Å hydrogen bondingI-PcTiO orientation through hydrogen-bonding
2.746 Å2.736 Å
ICPP-3, New Orleans, July 12, 2004
Mol. Structures: Group CN8bis (Pc2M)
N
N
N
N
N
N
N
N
N
N
N
N
NN
N
M
N
M
CCDC Molecule spacegroup angle [˚]
DPCYTH03 Pc2Th C2/c 37
DPCYTH Pc2Th C2/c 38
PHALCU* Pc2U C2/c 37
JONZAN Pc2Ce C2/c 38
SNPTCY01 Pc2Sn C2/c 38
DPCYTH01 Pc2Th C2/c 38
CIZGIB02 Pc2Nd {} C2/c 38
GAWBEL Pc2Gd P212121 ca. 41
ZAKZOA Pc2In P212121 41.2
DULZAL Pc2Lu {} P212121 41
GAWBAH Pc2LuH P212121 41
SNPTCY Pc2Sn P212121 42
YUHSUP Pc2Er {} P4/nnc 41.4
CIZGIB08 Pc2Nd P4/nnc 41.3
KOBRUO02 Pc2Pr P4/nnc 41.7
ZUWDAW [Pc2Bi][CH2Cl2] Pnma 45
ZEHTUB [Pc2La][CH2Cl2] Pnma 45
DICBUM [Pc2Lu][CH2Cl2] Pnma 45
JUVJIT [Pc2Y][CH2Cl2] Pnma 45
until now: defined by staggering angle but: angle depends on which units are used
angle corresponds to crystal structure
staggering angle is not amolecular property
bisphthalocyanines
ICPP-3, New Orleans, July 12, 2004
Arrangements: Group CN8bis (Pc2M)
A 1
1
2
2
A1
A2
-Pc2Pr
Pc2Ce
-Pc2Er
[Pc2Lu][CH2Cl2]
12
ICPP-3, New Orleans, July 12, 2004
Arrangements: Group CN8bis (Pc2M)
-Pc2Pr (A1)Pc2Ce (A2) [Pc2Lu][CH2Cl2]
(12)
ICPP-3, New Orleans, July 12, 2004
Final remarks
Further reading:M.K. Engel, J. Porph. Phthalocyanine, in preparationM.K. Engel, in "The Porphyrin Handbook",Vol. 20, 2003, 1-246P. Erk et al., CrystEngComm, 2004, accepted
The central atom together with axial ligands controlsmolecular structure and arrangement in the solid-state.
Phthalocyanines like to slip-stack.
Hydrogen-bonding is a major force.
Molecular properties (deformation) depend on the crystal arrangementcalculation of crystal structures need to use non-rigid molecules
This talk covered only pure materials, no mixtures. Co-crystallizingmaterials (impurities, solvents) can strongly influence the crystalstructure.
ICPP-3, New Orleans, July 12, 2004
Thank you
To you for listening.
To Prof. Heiner Homborg for many discussions and giving me accessto his unpublished crystal structures.
To Dr. Peter Erk for preprints and unpublished structures.
To Prof. Bob Scheidt for his work in porphyrin crystal structures whichgave me many ideas for phthalocyanine crystal structures.
To Dainippon Ink and Chemicals for having interest in my phthalocyanineresearch and allowing me to participate at this conference.
Michael Klaus [email protected]
http://phthalo.mkengel.de/pcrev.htm
ICPP-3, New Orleans, July 12, 2004