of 4
Supporting Information
for
Adv. Funct. Mater.,
DOI: 10.1002/adfm.202202710
Tuning the Performance of Negative Tone Electron
Beam Resists for the Next Generation Lithography
Scott M. Lewis
,* Guy A. DeRose
, Hayden R. Alty
,
Matthew S. Hunt
, Nathan Lee
, James A. Mann
, Richard
Grindell
,
Alex Wertheim, Lucia De Rose
, Antonio
Fernandez
, Christopher A. Muryn
,
George F. S.
Whitehead
,
Grigore A. Timco, Axel Scherer
, and
Richard
E. P. Winpenny
1
SUPPORTING INFORMATION:
Tuning the performance of negative tone electron beam resists for the next generation
lithography
Scott M. Lewis,
a,b,c
* Guy A. DeRose,
b
Ha
yden R. Alty,
a
Matthew S. Hunt,
b
Nathan Lee,
b
J.
A. Mann,
a
Richard Grindell,
c
Alex
Wertheim,
b
Lucia De Rose
b
, Antonio Fernandez,
a
Christopher A. Muryn,
a
George F. S. Whitehead
a
, Grigore A. Timco,
a
Axel Scherer
b
and
Richard E. P. Winpenny
a,c
*
a
Department of Chemistry and Photon Science Institute, The University of Manchester,
Oxford Road, Manchester M13 9PL, United Kingdom; E
-
mail:
scott.lewis@manchester.ac.uk
or
slewis2@caltech.edu
b
The
Kavli Nanoscience Institute, California Institute of Technology, 1200 East California
Boulevard, 107
81, Pasadena, CA USA 91125.
C
Sci
-
Tron Ltd, 34 High Street, Aldridge, Walsall WS9 8LZ, United Kingdom.
Experimental
Section
All reagents and solvents
used to synthesise the functionalised rings and linkers were
commercially available and used as received.
Synthesis of
1
has been published
previously.
1
Synthesis of
[NH
2
(CH
2
-
CH=CH
2
)
2
][Cr
7
NiF
8
(O
2
C
t
Bu)
16
]
2
Compound
2
was synthesized in a similar manner to
1
.
Diallyamine (2.5 g) was added t
o
pivalic acid (45g) in
a
Teflon flask then CrF
3
.
4H
2
O (12.0 g)
and 2NiCO
3
.
3Ni(OH)
2
.4H
2
O (2.0
g)
were added
. The flask
was
heated in an oil bath at 160 ºC for 24 h while stirring. During
this period a green microcrystalline product was formed. After this the flask was cooled to r.t.
and acetone (70 mL) was added with stirring. After 1 h the product was collected by filtration
and washed copiously with acetone (5
x
30 ml), and then extracted with
pentane (
100 ml
)
.
The
solution was filtered
and the
filtrate diluted with acetone
(50 ml)
. Then solvents
were
then
removed on
a
rotary evaporator, and
the
microcrystalline product washed with
acetonitrile (3
x
15 ml) and acetone (3 x 15 ml) and dried
i
n air.
The p
roduct was further
purified on
a
silica column by removing the fraction which mov
ed with 100%
t
oluene. Yield
:
2
20g for C
86
H
156
Cr
7
F
8
N
1
Ni
1
O
32
: (Elem. Anal. (calc./exp.): C (45.09/45.13), H (6.86/6.88),
N(0.61/0.62), Ni(2.56/2.61) and Cr (15.89/15.82); MS ES(+)
100%
-
[M+Na
+
]
+
-
2313.55,
45%
-
[M+H
+
]
+
-
2291.57
Synthesis of
[NH
2
(CH
2
-
CH=C
H
2
)
2
][Cr
7
NiF
8
(O
2
C
t
Bu)
15
(O
2
CC
5
H
4
N
-
HgCl
2
)]
3
An
iso
-
nicotinate ligand was added to
2
using the procedure outlined previously.
2
This gives
[NH
2
(CH
2
-
CH=CH
2
)
2
][Cr
7
NiF
8
(O
2
C
t
Bu)
15
(O
2
CC
5
H
4
N)]
2
-
Nic
.
Compound
2
-
Nic
(
0.5
g,
0.216
mmol)
and HgCl
2
(
0.0704
g,
0.259
mmol)
w
ere
dissolved in
a
1:1 (v/v) mixture of toluene and THF (20 mL)
.
T
he solution was stirred at RT for 2 h
; at that
point the solution was clear
. The solvent was
removed
under reduced pressure and hexane
(
10
mL)
was added to the residue and the soluti
on was filtered. The solvent was removed from the
filtrate and it yielded
0.224
g of
crystalline
solid
3
(
40
% yield based on
2
-
Nic
)
.
Crystals of
3
were grown from slow evaporation of a hexane solution at RT.
C
88
H
146
Cr
7
F
8
N
3
Ni
1
O
32
Hg
2
Cl
4
:
(Elem. Anal.
(calc./exp.): C(36.75/37.78), H(5.12/5.32), N(1.46/1.41), Cr(12.66/12.76),
Ni(2.04/1.85) and Cl(4.93/4.01).
Data for
3
were collected on a Rigaku FR
-
X DW diffractometer equipped with VariMAX
optics, a
4
-
circle
kappa AFC
-
11 goniometer and an Oxford Cryostr
eam 800 plus, using MoKα
radiation at a temperature of 100K. Data were collected and reduced using CrysAlisPro
v171.42 and the structural model was solved and refined using ShelX
-
20XX implemented
through Olex2. Similar moieties were refined to have similar
1,2
-
and 1,3
-
bond distances.
Disorder was modelled where possible. Nickel was modelled as disordered over the two
chromium sites sharing the same edge as the substituted isonicotinate moiety, based on the
refined atomic displacement parameters and as thi
s is the expected location based on the
relative ligand exchange kinetics of nickel (II) vs chromium (III) for substitution of pivalate
with isonicotinate.
3
Crystallographic information for
3
Identification code
rrepw496
Empirical formula
C
201
Cl
4
Cr
14
F
16
H
365
Hg
2
N
4
Ni
2
O
64
Formula weight
5554.35
Temperature/K
100.01(13)
Crystal system
monoclinic
Space group
I2/a
a/Å
34.0308(8)
b/Å
16.4899(3)
c/Å
50.4429(9)
α/°
90
β/°
100.7003(19)
γ/°
90
Volume/Å
3
27814.5(9)
Z
4
ρ
calc
g/cm
3
1.326
μ/mm
-
1
1.868
F(000)
11500.0
Crystal size/mm
3
0.25 × 0.185 × 0.083
Radiation
Mo Kα (λ = 0.71073)
2Θ range for data collection/°
3.088 to 58.678
Index ranges
-
46 ≤ h ≤ 43,
-
13 ≤ k ≤ 21,
-
58 ≤ l ≤ 67
Reflections collected
79958
Independent reflections
32309 [R
int
= 0.0581, R
sigma
= 0.0946]
Data/restraints/parameters
32309/7328/1658
Goodness
-
of
-
fit on F
2
1.030
Final R indexes [I>=2σ (I)]
R
1
= 0.0964, wR
2
= 0.2730
Final R indexes [all data
]
R
1
= 0.1582, wR
2
= 0.3062
Largest diff. peak/hole / e Å
-
3
1.20/
-
1.54
1.
F. K. Larsen, E. J. L. McInnes, M. H. El, J. Overgaard, S. Piligkos, G. Rajaraman, E.
Rentschler, A. A. Smith, G. M. Smith, V. Boote, M. Jennings, G. A. Timco
, R. E. P.
Winpenny,
Angew. Chem. Int. Ed.
,
2003
,
42
, 101.
2. G. A. Timco, S. Carretta, F. Troiani, F. Tuna, R. J. Pritchard, C. A. Muryn, E. J. L.
McInnes, A. Ghirri, A. Candini, P. Santini, G. Amoretti, M. Affronte, R. E. P. Winpenny,
Nat
.
Nanotechnol
.,
2008
,
4
, 173.