Transcript Phthalocyanines: From Molecular Structures to Solid

Phthalocyanines
From Molecular Structures to Solid-state
Arrangements
Molecular properties  Solid-state properties
PcCu
b-PcCuMolecular
is greenishStructures
blue
Classification
of Phthalocyanine
e-PcCu is reddish
Arrangement of the Phthalocyanine
Units inblue
Solid-state
Phthalocyanines:
Structure-Property Relationships
Start: Basic information about Phthalocyanine Molecular
Structures
Dr. Michael Klaus ENGEL ([email protected])
Dainippon Ink & Chemicals, Inc.
Central Research Laboratories; Sakura-shi, Japan
ICPP-3, New Orleans, July 12, 2004
Molecular Structures: Basics
1
X
2
N 3
N
X
M
X
N
X=CH: Tetrabenzoporphyrin: TBPH2
1) 139.0 pm
2) 249.5 pm; 127.9°
3) 295.5 pm
4) 688.6 pm
4
N
X
Nbr
molecular
axis
Ni
molecular
axis
X=N: Phthalocyanine: PcCo
1) 131.7 pm
2) 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)
ICPP-3, New Orleans, July 12, 2004
Molecular Structures: Basics
Coord.Nr.
Oxid.Nr.
4
2
5
2, 3, 4, 5
Geometry
square
planar
square
pyramidal
N
N
N
N
X
N
N
Mol.Sym.
Expl.
D4h
PcCu
C4v
PcSn
PcAlCl
PcTiO
PcReN
PcSiCl2
PcMoOCl
N
N
X
6tr
4, 5, 6
octahedral
N
N
N
N
Oh
X
6cis
7cis
4
5
trigonal
prismatic
capped
trigonal
prismatic
X
X
N
N
N
N
X
X
X
N
N
N
8cis/8bis
3, 4
cubic
8cis/8bis
3, 4
square
antiprismatic
N
PcNbCl3
N
Oh
[Pc2La]-
D4d
Pc2Zr
N
N
N
N
N
N
ICPP-3, New Orleans, July 12, 2004
C2v
N
N
N
PcNbCl2
N
N
N
D3h
N
Molecular Structures: Monomers
Monomeric phthalocyanines with planar macrocycle and identical faces
CN1
CN4
CN6tr
Monomeric phthalocyanines with bent macrocycle and different faces
CN5
CN5
CN7cis
CN8cis
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CN6cis
Molecular Structures: Dimers
Bis- and trisphthalocyanines with bent macrocycles
H
CN8bis
CN8bis
CN8bis
Dimeric phthalocyanines with planar or bent macrocycles
CN5
CN5
CN7cis
CN6cis
ICPP-3, New Orleans, July 12, 2004
CN6tr
CN8cis
Increased possibilities of interactions
Aromatic hydrocarbons:
Interaction between aromatic macrocycles: p-p interactions and H-p
interactions
Phthalocyanines additional interaction
possibilities due to the presence of
heteroatoms.
N
N
N
N
M
N
N
N
N
ICPP-3, New Orleans, July 12, 2004
Hydrogen atoms  electronegative atoms
Nitrogen atoms  hydrogen atoms
 axial ligands
 central atoms
Central atoms and axial ligands
 central atoms
 axial ligands
 nitrogen atoms
Arrangements: Group CN4 (PcM)
4 Basic overlap geometries
a-PcPt
b-PcH2
a-PcCu
x1-PcH2
the big confusionoverlap along N molecular axis
overlap along Nbr molecular axis
i
intermolecular bonding between Nbr and center stabilizes b-polymorphs
ICPP-3, New Orleans, July 12, 2004
Arrangements: Group CN4 (PcM)
Orientation of phthalocyanines in neighboring columns
a-PcPt
a-PcCu
2.7044 Å
Herringbone stacking
b-PcH2
x1-PcH2
2.6465 Å
S2 screw axis
Intercolumnar hydrogen-bonding
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intercolumnar distances
N…H > 3.2 Å
much weaker bonding
Arrangements: Group CN4 (PcM)
a-PcPt
g-PcPt 3.0143
2.6134ÅÅ
b-PcH2
3.0499 Å
(Nbr)
(Ni)
2.8408 Å
x1-PcH2
a-PcCu
ICPP-3, New Orleans, July 12, 2004
x2-PcH2
x1-PcH2
Arrangements: Group CN6tr (PcMX2)
overlap in CN4
much smaller in CN6tr
spatial need of axial ligands
Intermol. hydrogen bonding
+ repulsive interaction
x1-PcH2
PcSnI2
ICPP-3, New Orleans, July 12, 2004
PcCoCl2
PcSnI2
Arrangements: Group CN6tr (PcMX2)
Network structure
view along the column axes
2.568 Å
a-PcGe(OH)2
Intercolumnar 
hydrogen bonding
Network structure
view along the column axes
b-PcGe(OH)2
Intercolumnar 
hydrogen bonding
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x1-PcH2
2.592 Å
Molecular Structures: Group CN5 (PcMX)
Why do some phthalocyanines have a saucer-shaped macrocycle ?
Lax
 = 180o
isoindole unit
Ca Ni M Ni Ca
N
M
Ni
N
Ca
Ni
N
Ni
Ni
180oM
Ni Ca
Ca Ni
Ca
turn around axis
through Ca
N
Ca Ni
Ni-Ctr
M
Ni Caconvex
face
saucer-shaped
Ni-M
 2 different faces
 each face leads to a different arrangement
ICPP-3, New Orleans, July 12, 2004
concave face
Arrangements: Group CN5 (PcMX)
convex
concave
Ni
Nbr
no shift
sheet-type (or brickstone) arrangement
columnar (slipped-stacked) arrangements
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layer-type arrangements
Arrangements: Group CN5 (PcMX)
molecular lego
+
ICPP-3, New Orleans, July 12, 2004

PcAlCl

PcZnCl
Nbr
no shift
layer-type convex
PcGaCl
Ni
+
+

concave
Hydrogen bonding
parallel not parallel
I-PcTiO
2.746 Å
2.736 Å
PcNbCl2
orientation
ca. 3.5
through
Å hydrogen
hydrogen-bonding
bonding
PcSnCl2
molecular deformation through hydrogen-bonding
ICPP-3, New Orleans, July 12, 2004
PcSn
flattening through
repulsive interaction
Mol. Structures: Group CN8bis (Pc2M)
bisphthalocyanines
N
N
N N
N
N
N
N
M
N
N
N
N
N N
N
a
Molecule
spacegroup
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 {b}
C2/c
38
GAWBEL
Pc2Gd
P212121
ca. 41
ZAKZOA
Pc2In
P212121
41.2
DULZAL
Pc2Lu {g}
P212121
41
GAWBAH
Pc2LuH
P212121
41
SNPTCY
Pc2Sn
P212121
42
YUHSUP
Pc2Er {a}
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
N
until now: defined by
staggering angle
but: angle depends on
which units are used
angle corresponds to
crystal structure
staggering angle is not a
molecular property
ICPP-3, New Orleans, July 12, 2004
a
angle [˚]
CCDC
Arrangements: Group CN8bis (Pc2M)
[Pc2Lu]
[CH2Cl2]
2
1
12
a-Pc2Er
2
A
Pc2Ce
A1
1
A2
b-Pc2Pr
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Arrangements: Group CN8bis (Pc2M)
Pc2Ce (A2)
ICPP-3, New Orleans, July 12, 2004
b-Pc2Pr (A1)
[Pc2Lu][CH2Cl2]
(12)
Final remarks
The central atom together with axial ligands controls
molecular structure and arrangement in the solid-state.
Phthalocyanines like to slip-stack.
Hydrogen-bonding is a major force.
Further reading:
Molecular
properties
(deformation)
depend on the
arrangement
M.K.
Engel,
J. Porph.
Phthalocyanine,
in crystal
preparation
calculation
of "The
crystal Porphyrin
structures need
to use non-rigid molecules
M.K.
Engel, in
Handbook",
Vol.
20,
2003,
1-246
This
talk
covered
only pure materials, no mixtures. Co-crystallizing
materials
(impurities,
solvents) can strongly
influence the crystal
P. Erk
et al.,
CrystEngComm,
2004, accepted
structure.
ICPP-3, New Orleans, July 12, 2004
Thank you
To you for listening.
To Prof. Heiner Homborg for many discussions and giving me access
to his unpublished crystal structures.
To Dr. Peter Erk for preprints and unpublished structures.
To Prof. Bob Scheidt for his work in porphyrin crystal structures which
gave me many ideas for phthalocyanine crystal structures.
To Dainippon Ink and Chemicals for having interest in my phthalocyanine
research and allowing me to participate at this conference.
Michael Klaus Engel
[email protected]
http://phthalo.mkengel.de/pcrev.htm
ICPP-3, New Orleans, July 12, 2004